CN110227478A - Cobalt/cobalt oxide/pucherite composite material method is prepared by spin coating calcining - Google Patents
Cobalt/cobalt oxide/pucherite composite material method is prepared by spin coating calcining Download PDFInfo
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- CN110227478A CN110227478A CN201910617247.0A CN201910617247A CN110227478A CN 110227478 A CN110227478 A CN 110227478A CN 201910617247 A CN201910617247 A CN 201910617247A CN 110227478 A CN110227478 A CN 110227478A
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- bivo
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000004528 spin coating Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000001354 calcination Methods 0.000 title claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 title description 4
- 239000010941 cobalt Substances 0.000 title description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 3
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 86
- 229910002451 CoOx Inorganic materials 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims abstract description 13
- 238000001548 drop coating Methods 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000005518 electrochemistry Effects 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 239000010408 film Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000002023 wood 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
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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—
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The present invention provides a kind of calcine by spin coating and prepares CoOx/BiVO4The method of composite material is by CoCl2CoCl is configured to ethyl alcohol2Ethanol solution；With micro syringe by CoCl2The uniform drop coating of ethanol solution in BiVO4On film, spin coating is carried out with sol evenning machine, then by the BiVO after uniform spin coating4Film is placed in Muffle furnace, is warming up to 280 ~ 320 DEG C, is calcined 1 ~ 1.5 hour, and CoO is madex/BiVO4Composite material, the composite material has the worm shape structure of load sheet, this structure effectively inhibits the compound of photo-generated carrier, accelerate the transmission rate of electrons and holes, therefore there is excellent photoelectrocatalysis water oxidation activity, it is used for oxygen evolution reaction using it as photo cathode material, shows excellent optical electro-chemistry and decomposes aqueous energy.And this spin coating production method is easy to operate, and Load Balanced is easy to large-scale use.
Description
Technical field
The present invention relates to a kind of pucherite (BiVO4) based composites more particularly to it is a kind of utilize spin coating technique load C oOx
The BiVO of nanoparticle4Based composites (CoOx/BiVO4) preparation method, urged mainly as photo cathode material for photoelectricity
Change and decomposes in water.
Background technique
With getting worse for shortage of resources and environmental pollution, Hydrogen Energy is increasingly subject to widely pay close attention to.Optical electro-chemistry is decomposed
Aquatic products hydrogen, which can be realized, converts solar energy into clean hydrogen.Photoelectrocatalysis decomposes the water oxidation reaction that water Anodic occurs
One four electronic transfer process is the rate-limiting step of reaction.Therefore, the conversion of efficient solar energy to Hydrogen Energy is realized, it is necessary to
Improve the reaction efficiency of anode.BiVO4As a kind of typical n-type semiconductor, forbidden bandwidth Eg is about 2.4eV, is had visible
Photolytic activity is often used as the anode that photoelectrocatalysis decomposes water.It is similar to all anode materials, slow water oxidation kinetics system
About BiVO4The reaction efficiency of anode, and then influence the reaction efficiency of photoelectrocatalysis water decomposition.In BiVO4Upper water load oxidation is urged
Agent can effectively improve BiVO4On water oxidizing reaction rate.
Oxide (the CoO of cobaltx) it is a kind of efficient water oxidation catalyst, it is commonly used to be supported on BiVO4Upper raising BiVO4
The reaction efficiency of anode.Conventional load CoOxMethod has the methods of hydro-thermal method, electro-deposition, ion sputtering, these methods or mistake
Journey is excessively complicated or cost is excessively high, is not suitable for large-scale application.Therefore, a kind of easy, cheap preparation CoO is foundx/
BiVO4The method of complex light anode is of great significance for converting solar energy on a large scale into Hydrogen Energy.
Summary of the invention
Spin coating technique load C oO is utilized the object of the present invention is to provide a kind ofxNanometer sheet prepares CoOx/BiVO4Composite material
Method.
One, CoOx/BiVO4The preparation of composite material
By CoCl2Being configured to concentration is 0.015 ~ 0.12 mol/LCoCl2Ethanol solution；With micro syringe by CoCl2Second
The uniform drop coating of alcoholic solution is in BiVO4On film, with sol evenning machine carry out spin coating (revolving speed be 5800 ~ 6200 r/min, the duration 20 ~
30s.), then by the BiVO after uniform spin coating4Film is placed in Muffle furnace, is warming up to 280 ~ 320 DEG C (5 DEG C/min of heating rate),
CoO is made in calcining 1 ~ 1.5 hourx/BiVO4Composite material.
Two, CoOx/BiVO4The characterization of composite material
Fig. 1 is BiVO4And CoOx/BiVO4Scanning electron microscope (SEM) photograph.As seen from Figure 1, BiVO4(a) worm shape surface texture is presented,
With uniform cellular structure, one layer of porous BiVO is formed on FTO electro-conductive glass4Nano thin-film.By scheming CoOx/BiVO4
(b) scanning electron microscope (SEM) photograph finds out, the CoO of synthesisx/BiVO4Composite material does not change BiVO4Worm shape structure, but
BiVO4Film surface forms one layer of CoOxNanometer sheet.
Fig. 2 is BiVO4、CoOx/BiVO4XRD diagram.BiVO in figure4For monoclinic phase BiVO4, CoOx/BiVO4Laminated film
Peak and BiVO4The peak of film is corresponding, CoO does not occurxPeak, this may be because load CoOxThe less original of amount
Cause.CoOx/BiVO4Peak intensity and BiVO4Compared to slightly weakening, the CoO of load is illustratedxAffect BiVO4Peak intensity.
Three, BiVO4、CoOx/BiVO4The photoelectrochemical behaviour of composite material is tested
Fig. 3 has recorded BiVO under illumination condition4, CoOx/BiVO4Linear sweep voltammetry curve.Under light conditions, pure BiVO4
1.23V vs.RHE(AM1.5G simulated solar irradiation irradiate) when density of photocurrent be 1.05 mA cm-2, composite material CoOx/
BiVO4Density of photocurrent irradiated in 1.23 V vs.RHE(AM1.5G simulated solar irradiations) when reach 2.7 mA cm-2, and it is pure
BiVO4(1.05 mA cm-2) compared to increasing 2.6 times.Illustrate CoOxLoad to BiVO4Surface on, make ABSORPTION EDGE red shift,
This has widened BiVO4To the light absorption range of solar spectrum, BiVO is improved4To the utilization efficiency of sunlight, and synthesize compound
Material forms p-n heterojunction, improves the separative efficiency of electrons and holes.CoOxIt is a kind of water oxidation promoters, its energy
It is enough to be quickly passed in hole in electrolyte solution, oxidation reaction occurs.
Fig. 4 shows the pure BiVO under no illumination4With 0.03,0.06,0.12-CoOx/BiVO4Linear sweep voltammetry
Curve.The results show that pure BiVO4With 0.03,0.06,0.12-CoOx/BiVO4The take-off potential of photo cathode material is in 1.23 V
It is respectively 2.3 V, 2.0 V, 1.8 V and 1.5 V under vs.RHE, the take-off potential of reaction to movable cathode, illustrates composite wood
Material reduces the overpotential of reaction.0.06-CoOx/BiVO4The take-off potential of photo cathode material reaction is to movable cathode 0.5
V, movement value is maximum, BiVO4Electrolysis water oxidation efficiency highest.
Fig. 5 is 0.06-CoOx/BiVO4Chopping the light linear sweep voltammetry curve.It can be seen that 0.06-CoOx/BiVO4It is multiple
Condensation material density of photocurrent of (irradiation of AM1.5G simulated solar irradiation) at 1.23 V vs.RHE is 2.7 mA cm-2, chopping the light
Density of photocurrent irradiated in 1.23 V vs.RHE(AM1.5G simulated solar irradiations) under also reach 2.7 mA cm-2.Illustrate compound
Material improves BiVO4Optical electro-chemistry water dispersible energy.
Fig. 6 is BiVO4And 0.06-CoOx/BiVO4Charge injection efficiency figure.By measuring in hole scavenger electrolyte
In photocurrent values, charge injection efficiency is calculated.We have found that CoOxCoating greatly improves BiVO4In 1.23 V
Vs. injection efficiency when RHE shows CoO from 30% to 50%xPromote the dynamics of electrode surface water oxygen.
In conclusion the present invention is in BiVO4The CoCl of a certain amount of concentration of spin coating on nano thin-film2Solution, by Muffle furnace
After middle calcining, CoCl2Form Co2O3、Co3O4, and it is successfully loaded BiVO4Membrane structure, so that N-shaped BiVO4Semiconductor is built into
For p-n heterojunction, CoO is formedx/BiVO4Composite material, the composite material have the worm shape structure of load sheet, and this structure has
Effect inhibits the compound of photo-generated carrier, accelerates the transmission rate of electrons and holes, therefore have excellent photoelectrocatalysis water
Oxidation activity is used for oxygen evolution reaction using it as photo cathode material, shows excellent optical electro-chemistry and decomposes aqueous energy.And
This spin coating production method is easy to operate, and Load Balanced is easy to large-scale use.
Detailed description of the invention
Fig. 1 is BiVO4SEM figure and CoOx/BiVO4Scanning electron microscope (SEM) photograph.
Fig. 2 is BiVO4、CoOx/BiVO4XRD diagram.
Fig. 3 has recorded pure BiVO under illumination condition4, CoOx/BiVO4Linear sweep voltammetry curve.
Fig. 4 has recorded pure BiVO under non-illuminated conditions4, CoOx/BiVO4Linear sweep voltammetry curve.
Fig. 5 is 0.06-CoOxChopping the light linear sweep voltammetry curve.
Fig. 6 is BiVO4And 0.06-CoOx/BiVO4Charge injection efficiency figure.
Specific embodiment
Below by specific implementation method to BiVO of the present invention4、CoOx/BiVO4The system of composite material (utilizing spin coating technique)
Standby and performance is described further.
Embodiment 1,0.06-CoOx/BiVO4The preparation of composite material
(1) preparation of BiOI film
BiOI film is prepared using cyclic voltammetry electro-deposition in three-electrode system.Platinum plate electrode is used as to electrode, Ag/
AgCl electrode is as reference electrode, and FTO electro-conductive glass is as working electrode (using preceding super with acetone, isopropanol, secondary distilled water
Sound cleans 40 min), voltage is set as 0V ~ -0.13V, sweep speed 5mV/s when electro-deposition, and scanning circle number is 10 circles,
After the completion of electro-deposition, dry with distilled water flushing and in air.Electro-deposition prepares the electrolyte quota process of BiOI film such as
Under:
A. it is poured into the beaker of 100 ml with the distilled water that graduated cylinder measures 50 ml；Then 3.3 ~ 3.4 gKI drugs are weighed, in magnetic
Under sub quickly stirring, drug is added in distilled water, transparent clear solution is formed.
B. with the nitric acid (HNO of 1 mol/L3) adjust KI solution pH value be 1.5 ~ 1.7；
C. 0.9 ~ 1 g, five water bismuth nitrate (Bi (NO is weighed3)3•5H2O) be added KI solution in, stir 15 min after, solution colour by
Gradually become orange red from blackish green；
D. 0.4 ~ 0.5 g 1,4-benzoquinone (C is weighed6H4O2), it is added in 20mL dehydrated alcohol, 15 min of stirring obtain pair of brown
Benzoquinones solution；
E. the ethanol solution of 1,4-benzoquinone is added dropwise in the orange-red solution in (c), is then vigorously agitated again 10 ~ 30 min.
(2) BiVO4The preparation of film
A. by 0.1 ~ 0.15g vanadyl acetylacetonate (VO (acac)2), it is added in the dimethyl sulfoxide (DMSO) of 2.5 ~ 3 ml and stirs
15 min are mixed, the dimethyl sulphoxide solution of vanadyl acetylacetonate is obtained；
B. the dimethyl sulphoxide solution that the vanadyl acetylacetonate of 100 μ L is measured with micro syringe drips on BiOI film；
C. there is the film in vanadium source to be put in Muffle furnace drop, 4 ~ 5 h are calcined at 450 ~ 500 DEG C；Temperature is cooled to room temperature, will be thin
Film takes out；
D. by the BiVO of formation4Film immerses a period of time in 1 mo/L NaOH solution, removes Bi2O3、V2O5Equal impurity, work as face
After color becomes faint yellow completely, BiVO is taken out with tweezers4Film, and the lye of attachment removal is removed wash with distilled water.
(3) CoOx/BiVO4The preparation of composite material
Take a certain amount of CoCl2, being configured to concentration is 0.06 mol/LCoCl2Ethanol solution；200 are measured with micro syringe
μL CoCl2Ethanol solution, uniform drop coating is in BiVO4Start sol evenning machine after film and carry out spin coating, revolving speed is 5800 ~ 6200 r/
Min continues 30s, then by the BiVO after uniform spin coating4Film is placed in Muffle furnace, in 300 DEG C of calcinings, 1 hour (heating rate
5 DEG C/min), form 0.06-CoOx/BiVO4Composite material.
(4) 0.06-CoOx/BiVO4Performance test
By 0.06-CoOx/BiVO4Composite material is used for optical electro-chemistry water decomposition reaction test, photoelectric current as photo cathode
Density 1.23Vvs.RHE(AM1.5G simulated solar irradiation irradiate) under reach 2.7mA cm-2。
Embodiment 2,0.03-CoOx/BiVO4The preparation of composite material
(1) preparation of BiOI film: with embodiment 1；
(2) BiVO4The preparation of film: with embodiment 1；
(3) 0.03-CoOx/BiVO4The preparation of composite material: CoCl2The concentration of ethanol solution be 0.03 mol/L, other are same
Embodiment 1；
(4) 0.03-CoOx/BiVO4Performance test: by 0.03-CoOx/BiVO4Composite material is used for photoelectricity as photo cathode
Chemical water decomposition reaction test, density of photocurrent 1.23Vvs.RHE(AM1.5G simulated solar irradiation irradiate) under reach
2.5mA cm-2。
Embodiment 3,0.12-CoOx/BiVO4The preparation of composite material
(1) preparation of BiOI film: with embodiment 1；
(2) BiVO4The preparation of film: with embodiment 1；
(3) 0.12-CoOx/BiVO4The preparation of composite material: CoCl2The concentration of ethanol solution be 0.12 mol/L, other are same
Embodiment 1；
(4) 0.12-CoOx/BiVO4Performance test: using composite material as photo cathode be used for optical electro-chemistry water decomposition reaction
Test, density of photocurrent 1.23Vvs.RHE(AM1.5G simulated solar irradiation irradiate) under reach 2.3mA cm-2。
Claims (4)
1. spin coating calcining preparation CoOx/BiVO4The method of composite material, it is characterised in that: be by CoCl2It is configured to ethyl alcohol
CoCl2Ethanol solution；With micro syringe by CoCl2The uniform drop coating of ethanol solution in BiVO4On film, carried out with sol evenning machine
Spin coating, then by the BiVO after uniform spin coating4Film is placed in Muffle furnace, is warming up to 280 ~ 320 DEG C, is calcined 1 ~ 1.5 hour, is made
CoOx/BiVO4Composite material.
2. spin coating calcining preparation CoO as described in claim 1x/BiVO4The method of composite material, it is characterised in that: CoCl2's
The concentration of ethanol solution is 0.015 ~ 0.12 mol/L.
3. spin coating calcining preparation CoO as described in claim 1x/BiVO4The method of composite material, it is characterised in that: sol evenning machine into
The revolving speed of row spin coating is 5800 ~ 6200 r/min, and the duration is 20 ~ 30s.
4. spin coating calcining preparation CoO as described in claim 1x/BiVO4The method of composite material, it is characterised in that: heating rate
For 5 DEG C/min.
Priority Applications (1)
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