CN108529557A - It is a kind of for the hole accumulation layer of photoanode surface, light anode composite construction and purposes - Google Patents
It is a kind of for the hole accumulation layer of photoanode surface, light anode composite construction and purposes Download PDFInfo
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- CN108529557A CN108529557A CN201810253809.3A CN201810253809A CN108529557A CN 108529557 A CN108529557 A CN 108529557A CN 201810253809 A CN201810253809 A CN 201810253809A CN 108529557 A CN108529557 A CN 108529557A
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- cobalt
- base oxide
- cobalt base
- accumulation layer
- light anode
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- 238000009825 accumulation Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims description 23
- 238000010276 construction Methods 0.000 title claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 48
- 239000010941 cobalt Substances 0.000 claims abstract description 48
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 48
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004528 spin coating Methods 0.000 claims abstract description 14
- 239000002250 absorbent Substances 0.000 claims abstract description 13
- 230000002745 absorbent Effects 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- 150000001868 cobalt Chemical class 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910003153 β-FeOOH Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- SGKOIECSMWMSTN-UHFFFAOYSA-N [N+](=O)([O-])[Fe]([N+](=O)[O-])[N+](=O)[O-] Chemical compound [N+](=O)([O-])[Fe]([N+](=O)[O-])[N+](=O)[O-] SGKOIECSMWMSTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 3
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 36
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 37
- 235000013495 cobalt Nutrition 0.000 description 29
- 239000010408 film Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- -1 tert-butyl alcohols Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
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- 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
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- 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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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of hole accumulation layer for photoanode surface, the hole accumulation layer is cobalt base oxide nano-particle layer.The present invention selects cobalt base oxide as hole storage layer so that photoanode surface stores suitable hole, promotes electric charge transfer, and reduces the probability of charge recombination, improves the photoelectric current of light anode.The present invention can obtain the cobalt base oxide of different valence state, realize the adjustment to hole storage layer hole storage capacity, can be suitable for different semiconductor light absorbents by selecting different presomas；In optimal technical scheme, spin-coating method, which prepares cobalt base oxide, can avoid secondary hydro-thermal from influencing the deterioration of iron oxide semiconductor light-absorption layer.
Description
Technical field
The invention belongs to novel energy resource material technology fields, and in particular to a kind of hole accumulation layer for photoanode surface,
Light anode composite construction and purposes.
Background technology
The process of photochemical catalyzing is specially：After light irradiates semiconductor catalyst, catalyst absorbs energy and is more than its band
The light of gap, photohole and electronics generate and move to catalyst surface therewith, and oxidation and reduction reaction occurs with water, generates oxygen
Gas and hydrogen.Photoelectrocatalysis is made production oxygen and the reaction of production hydrogen occur respectively in anode and cathode, is more had using semiconductor as optoelectronic pole
Conducive to the separation and collection of gas.Therefore, photoelectrocatalysis water decomposition is the hand for the great potential for converting solar energy into chemical energy
Section, but lower energy conversion efficiency restricts its application.
Photoelectrocatalysis water decomposition includes production hydrogen and production two half-reactions of oxygen, wherein production oxygen reaction is related to answering for four holes transfer
Miscellaneous process becomes the conditioning step of overall reaction.Therefore the development of high-performance optical anode is most important.
In recent years, become the popular method of its performance of raising in photoanode surface modification hole storage layer.But the prior art
In common hole storage layer MoO3It is in alkaline solution and unstable, significantly limit its application.Therefore, develop a kind of energy
The hole storage layer being stabilized in alkaline solution is extremely necessary.
In addition, the hole storage volume of hole storage layer is an important factor for influencing its effect.On the one hand, hole storage layer
Hole is extracted from semiconductor, realizes being spatially separating for photo-generate electron-hole, extends the service life of photohole.On the other hand,
The hole concentration of photoanode surface can be improved in hole storage layer, to promote the rate for the production oxygen reaction that four holes participate in, promotes
The transfer of photohole.However, hole storage layer also brings along negative effect.The hole largely accumulated in this layer can inhale strongly
Draw the electronics in semiconductor, brings the serious compound of photo-generated carrier.It can be seen that the hole of photoanode surface storage can both promote
Into electric charge transfer, and charge recombination can be aggravated, the competition of the two decides the final performance of light anode.Studies have shown that above-mentioned competing
Strive behavior is influenced by photoanode surface hole storage volume.Therefore, hole of the development with suitable hole storage volume is stored up
It is extremely necessary to deposit layer.
Invention content
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of holes for photoanode surface to deposit
Reservoir, the hole accumulation layer are cobalt base oxide nano-particle layer.
The present invention can be obtained using cobalt base oxide nano-particle layer as hole accumulation layer by the valence state of selection cobalt
Hole storage layer with different hole storage capacitys；Meanwhile cobalt base oxide has good stability in alkaline solution.
Preferably, in the hole accumulation layer, the distribution density of cobalt base oxide is 0.5~2 μ g/cm2, such as 0.6 μ g/
cm2、0.8μg/cm2、1μg/cm2、1.5μg/cm2、2μg/cm2Deng.
In the storage layer of hole, if the distribution density of cobalt base oxide is excessive, the light absorption of semiconductor may be influenced, it is too small then
Hole is set to store effect unobvious.
Preferably, the cobalt base oxide includes cobaltosic oxide or cobalt black.
Preferably, when the cobalt base oxide is cobaltosic oxide, distribution density in the accumulation layer of hole is 1~
2μg/cm2。
Preferably, when the cobalt base oxide is cobalt black, distribution density in the accumulation layer of hole is 0.5~
0.6μg/cm2。
Preferably, the grain size of the cobalt base oxide nano particle be 3~6nm, such as 3.5nm, 4.0nm, 4.5nm,
5.0nm, 5.5nm etc..
The present invention is not specifically limited the semiconductor light absorbent in light anode, any type those skilled in the art
The semiconductor light absorbent that can be obtained is used equally for the present invention.
Preferably, the semiconductor light absorbent in the light anode is alpha-ferric oxide film.
Preferably, when the semiconductor light absorbent is alpha-ferric oxide film, the hole accumulation layer is four oxidations three
Cobalt nano-particle layer.
When the semiconductor light absorbent is alpha-ferric oxide film, the hole accumulation layer is cobaltosic oxide nano particle
Layer can ensure suitable hole storage capacity, promote the photoelectric current of light anode.
The two of the object of the invention are to provide a kind of light anode composite construction, and the light anode includes electrically conducting transparent substrate, raw
The semiconductor light absorbent being longer than in the electrically conducting transparent substrate, and it is covered in the hole storage on semiconductor light absorbent surface
Layer, one of for the purpose of the hole accumulation layer described in the hole accumulation layer for photoanode surface.
In light anode composite construction provided by the invention, semiconductor absorber luminous energy generates light induced electron and hole；Photoproduction
Hole is extracted by hole storage layer, reaches light anode-electrolyte interface, and oxidation water generates oxygen；Light induced electron is collected by substrate,
It is reached to electrode by external circuit, reductive water generates hydrogen.
Preferably, the electrically conducting transparent substrate includes FTO transparent conducting glass or transparent electro-conductive glass.
The three of the object of the invention are to provide a kind of preparation method of light anode composite construction described in the second purpose, the method
Include the following steps：
(1) β-FeOOH films are grown in the precalculated position of electrically conducting transparent substrate by hydro-thermal reaction, is made a reservation for after calcining
Position grows the electrically conducting transparent substrate for having alpha-ferric oxide film；
(2) cobalt base oxide nano particle is prepared, and is dispersed in solvent and prepares cobalt base oxide nano particle point
Dispersion liquid；
(3) the cobalt base oxide nanoparticulate dispersion is coated to alpha-ferric oxide film surface, is obtained after removing solvent
To light anode composite construction.
Preferably, step (1) described " β-FeOOH films are grown in electrically conducting transparent substrate by hydro-thermal reaction " is specific
Step is：
The precalculated position of electrically conducting transparent substrate is exposed in the aqueous solution containing molysite and sodium salt by (1a), and titanium source point is added dropwise
Dispersion liquid carries out hydro-thermal reaction by mixed solution under closed environment, and obtaining precalculated position growth has the transparent of β-FeOOH films
Conductive substrates.
Preferably, the molysite includes trivalent iron salt, preferably ferric trichloride or trinitro- iron, a concentration of 0.05~
0.15mol/L, for example, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.10mol/L, 0.11mol/L,
0.12mol/L, 0.13mol/L, 0.14mol/L etc..
Preferably, it is preferable that in the aqueous solution containing molysite and sodium salt, a concentration of 0.05~0.2mol/ of sodium salt
L, such as 0.06mol/L, 0.08mol/L, 0.10mol/L, 0.13mol/L, 0.15mol/L, 0.17mol/L, 0.19mol/L
Deng.
Preferably, the titanium source includes titanium tetrachloride.
Preferably, the dispersant of the titanium source dispersion liquid includes ethyl alcohol.
Preferably, atomicity accounts for the 1%~5% of the sum of iron atom and titanium atom number in the mixed solution, such as
1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% etc..
Preferably, the temperature of the hydro-thermal reaction is 110~130 DEG C (such as 115 DEG C, 120 DEG C, 125 DEG C etc.), and the time is
3.5~4.5h (such as 3.8h, 4.0h, 4.3h etc.)；It is preferred that the temperature of the hydro-thermal reaction is 120 DEG C, time 4h.
Preferably, the exposure chamber in the precalculated position is to cover non-predetermined position by high temperature gummed tape to realize precalculated position
Exposure.
Preferably, the temperature of step (1) described calcining is 550~800 DEG C (such as 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C
Deng), the time is 10min~120min (such as 20min, 40min, 60min, 80min, 100min etc.)；It is preferred that the temperature calcined
It is 600 DEG C, time 60min.
Preferably, the preparation method of described " cobalt base oxide nano particle " is specially：
The dispersion in organic solvent of cobalt salt is carried out hydro-thermal reaction by (2a), obtains hydro-thermal reaction product；Hydro-thermal reaction is produced
Cobalt base oxide nano particle is obtained after object centrifugation, washing, drying.
Preferably, the cobalt salt includes divalent cobalt, preferably cobalt acetate or acetylacetone cobalt.
Preferably, when the cobalt salt is cobalt acetate, the organic solvent of the dispersion in organic solvent of the cobalt salt is ethyl alcohol,
In the dispersion liquid also be added with ammonium hydroxide, the hydrothermal temperature be 100~150 DEG C (such as 110 DEG C, 120 DEG C, 130 DEG C,
140 DEG C etc.), the reaction time is 2.5~3.5h (such as 2.6h, 2.8h, 3.3h etc.).
It is further preferred that when the cobalt salt is cobalt acetate, the preparation method of the reaction system is：Cobalt acetate is molten
In ethyl alcohol, ammonium hydroxide is added under stirring condition, is kept stirring 10min.
When the cobalt salt is cobalt acetate, ammonium hydroxide provides weakly alkaline environment for the hydro-thermal reaction.
Preferably, when the cobalt salt is acetylacetone cobalt, the hydrothermal temperature is 180~200 DEG C (such as 185
DEG C, 190 DEG C, 195 DEG C etc.), the reaction time be 12~20h (such as 15h, 16h, 17h, 18h, 19h etc.).
When the cobalt salt be acetylacetone cobalt when, hydrothermal temperature be 180~200 DEG C can obtain it is suitably sized and
Crystallinity (temperature is too low, and crystallinity is bad, and temperature is excessively high, becomes large-sized)
Preferably, the rotating speed of the centrifugation is 7000~9000rpm (such as 7500rpm, 8000rpm, 8500rpm etc.),
It is preferred that 8000rpm.
Preferably, the solvent of the cleaning is ethyl alcohol.
Preferably, the dispersant of step (2) the cobalt base oxide nanoparticulate dispersion be ethyl alcohol and/or acetic acid, it is excellent
It is 3 to select the mixed solvent of ethyl alcohol and acetic acid, further preferred volume ratio:7 ethyl alcohol and the mixed solvent of acetic acid.
Preferably, in step (2) the cobalt base oxide nanoparticulate dispersion, the dispersion of cobalt base oxide nano particle
A concentration of 0.1~2mg/mL (such as 0.2mg/mL, 0.5mg/mL, 0.8mg/mL, 1.0mg/mL, 1.2mg/mL, 1.5mg/mL,
1.7mg/mL, 1.9mg/mL etc.).
Preferably, the mode of the coating includes arbitrary a kind or at least two kinds of of the combination in spin coating, drop Tu, dip-coating, excellent
Select spin coating.
Preferably, the step of spin coating is：30 μ L cobalt base oxide nanoparticulate dispersions are added dropwise to center of turntable,
After 8~10s being rotated with the rotating speed of 800~1200rpm, then with 18~23s of rotating speed rotation of 2500~3500rpm.
The step of specific spin coating, enables to cobalt base oxide nano particle uniformly to coat, and rotating speed is excessively high to make nanometer
Grain is detached from film, and rotating speed is too low to make nano particle not can be uniformly dispersed.
Preferably, the method for removing solvent includes drying, and 0.8~1.2h is dried preferably at 95~105 DEG C.
The four of the object of the invention are to provide a kind of application of the compound light anode as described in the third purpose, the compound
Light anode decomposes water for optical electro-chemistry.
The five of the object of the invention are to provide a kind of device of photochemical catalyzing, for the purpose of the working electrode of described device it
Compound light anode described in three.
Compared with prior art, the present invention has the advantages that：
(1) present invention selects cobalt base oxide as hole storage layer so that and photoanode surface stores suitable hole,
Electric charge transfer is promoted, and reduces the probability of charge recombination, improves the photoelectric current of light anode.
(2) present invention can obtain the cobalt base oxide of different valence state, realize to hole by selecting different presomas
The adjustment of storage layer hole storage capacity can be suitable for different semiconductor light absorbents；
(3) in optimal technical scheme, spin-coating method, which prepares cobalt base oxide, can avoid secondary hydro-thermal from partly leading iron oxide
The deterioration of body light-absorption layer influences.
Description of the drawings
Fig. 1 gives the high-resolution-ration transmission electric-lens figure of the light anode composite construction of the preparation of embodiment 1；
Fig. 2 gives the high-resolution-ration transmission electric-lens figure of the light anode composite construction of the preparation of embodiment 5.
Fig. 3 gives embodiment 1, the hole storage volume test result of embodiment 5 and comparative example 1.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of light anode, includes the following steps：
(1) prepare conductive substrates：
By 2cm × 2.5cm sizes cutting FTO (SnO of doping fluorine2Transparent conducting glass), successively isopropanol, acetone,
Each ultrasound 15min, is then dried up with nitrogen in ethyl alcohol.Clean FTO conducting surfaces top about 0.5cm is covered with high temperature gummed tape,
The back side is all covered with high temperature gummed tape, is vertically placed in 50mL water heating kettles, and high temperature gummed tape is used in combination to fix its position；
(2) growth of β-FeOOH films：
By 0.2703g FeCl3·6H2O and 0.1420g Na2SO420mL is dissolved in three times in water, and 0.3mL TiCl are added4It is molten
(formula is 0.11mL TiCl to liquid4+ 10mL ethyl alcohol), obtain mixed solution；Then the mixed solution of preparation is poured into and has been placed with
It in the water heating kettle of FTO, is put in baking oven after tight encapsulation, setting temperature is 120 DEG C, continues 4h；It waits for throwing off base after reaction
High temperature gummed tape on bottom is used in combination water flushing three times, then uses N2Drying；
(3) β-FeOOH films are made it be converted into alpha-ferric oxide film by high-temperature calcination：
Muffle furnace is risen to 600 DEG C, then step 2 gained sample is positioned on one piece of smooth ceramic wafer, then
It is sent into Muffle furnace with hawkbill, after calcining 1h, sample is taken out from 600 DEG C of Muffle furnace, is cooled down at room temperature；
(4) cobalt/cobalt oxide nano particle is synthesized：
By 2mmol Co (CH3COO)2·4H2O is dissolved in 20mL ethyl alcohol, and 3.2mL 25% is added dropwise under vigorous stirring
Ammonium hydroxide, then be transferred in water heating kettle after persistently stirring 10min in air；Then after water heating kettle tightly being encapsulated, it is put in baking oven
In, setting temperature is 120 DEG C, continues 3h；After reaction, gained is precipitated and 5min is centrifuged with 8000rpm, then washed with ethyl alcohol
3 times, it is put into vacuum drying oven later, it is Co to be dried at room temperature for the product being prepared about for 24 hours3O4(grain size is 3 for nano particle
Within the scope of~6nm), Co valence states are based on+III valences；
(5) uniform dispersion is made in cobaltosic oxide nano particle：
Then cobaltosic oxide powder 10mg obtained by step (4) is taken, 3.5mL glacial acetic acid and 1.5mL ethyl alcohol is added, ultrasound is straight
Evenly dispersed to sample, bottom obtains the cobaltosic oxide nano particle dispersion of 2mg/mL without visible solid；
(6) spin-coating method prepares cobaltosic oxide/alpha-ferric oxide compound light anode：
Step 3 gained alpha-ferric oxide film is fixed on sol evenning machine turntable, take 30 μ L drops of dispersion liquid obtained by step (5) in
Thin film center, setting condition are that 3000rpm continues 30s after 1000rpm continues 10s.Gained sample is dried in Muffle furnace, and 100
DEG C continue 1h, obtain light anode composite construction.In the hole storage layer of the light anode composite construction, the distribution of cobaltosic oxide
Density is 2 μ g/cm2。
Fig. 1 gives the high-resolution-ration transmission electric-lens figure of the light anode composite construction of the preparation of embodiment 1.
Embodiment 2~4
Difference lies in the concentration of adjustment cobaltosic oxide nano particle dispersion is respectively 0.1mg/cm with embodiment 13
(embodiment 2), 0.5mg/cm3(embodiment 3), 1mg/cm3(embodiment 4) so that the hole storage layer of light anode composite construction
In, the distribution density of cobaltosic oxide is 0.1 μ g/cm2(embodiment 2), 0.5 μ g/cm2(embodiment 3), 1 μ g/cm2(embodiment
4)。
Embodiment 5
A kind of preparation method of light anode, includes the following steps：
Step (1)~step (3) is same as Example 1；
(4) cobalt/cobalt oxide nano particle is synthesized：
It takes 1mmol acetylacetone cobalts (II) to be added in the 28mL tert-butyl alcohols and obtains mixture；Then obtained mixture is existed
It is transferred in water heating kettle after stir about 10min in air, baking oven is put into after sealing, 190 DEG C of temperature is set, continue 12h；Reaction knot
Gained is precipitated after beam, 5min is centrifuged with 8000rpm, then washed 3 times with ethyl alcohol, is put into vacuum drying oven later, be dried at room temperature for
About for 24 hours, the product being prepared is CoO nano particles (grain size is within the scope of 3~6nm), and Co valence states are based on+II；
(5) uniform dispersion is made in CoO nano particles：
CoO nano particle 10mg obtained by step (4) are taken, 3.5mL glacial acetic acid and 1.5mL ethyl alcohol are added, ultrasound is until sample
Evenly dispersed, bottom obtains 2mg/ml CoO nanoparticulate dispersions without visible solid；
(6) spin-coating method prepares cobalt black/alpha-ferric oxide compound light anode：
Alpha-ferric oxide film obtained by step (3) is fixed on sol evenning machine turntable, 30 μ L drops of dispersion liquid obtained by step (5) are taken
In thin film center, setting condition is that 3000rpm continues 30s after 1000rpm continues 10s；Then by gained sample in Muffle furnace
Drying, 100 DEG C of lasting 1h, obtains light anode composite construction.In the hole storage layer of the light anode composite construction, cobalt black
Distribution density be 2 μ g/cm2。
Fig. 2 gives the high-resolution-ration transmission electric-lens figure of the light anode composite construction of the preparation of embodiment 5.
Embodiment 6~8
Difference lies in the concentration of adjustment cobalt black nanoparticulate dispersion is respectively 0.1mg/cm with embodiment 53
(embodiment 6), 0.5mg/cm3(embodiment 7), 1mg/cm3(embodiment 8) so that the hole storage layer of light anode composite construction
In, the distribution density of cobalt black is 0.1 μ g/cm2(embodiment 6), 0.5 μ g/cm2(embodiment 7), 1 μ g/cm2(embodiment 8).
Comparative example 1
A kind of preparation method of light anode, includes the following steps：
(1) prepare conductive substrates：
By 2cm × 2.5cm sizes cutting FTO (SnO of doping fluorine2Transparent conducting glass), successively isopropanol, acetone,
Each ultrasound 15min, is then dried up with nitrogen in ethyl alcohol.Clean FTO conducting surfaces top about 0.5cm is covered with high temperature gummed tape,
The back side is all covered with high temperature gummed tape, is vertically placed in 50mL water heating kettles, and high temperature gummed tape is used in combination to fix its position；
(2) growth of β-FeOOH films：
By 0.2703g FeCl3·6H2O and 0.1420g Na2SO420mL is dissolved in three times in water, and 0.3mL TiCl are added4It is molten
(formula is 0.11mL TiCl to liquid4+ 10mL ethyl alcohol), obtain mixed solution；Then the mixed solution of preparation is poured into and has been placed with
It in the water heating kettle of FTO, is put in baking oven after tight encapsulation, setting temperature is 120 DEG C, continues 4h；It waits for throwing off base after reaction
High temperature gummed tape on bottom is used in combination water flushing three times, then uses N2Drying；
(3) β-FeOOH films are made it be converted into alpha-ferric oxide film by high-temperature calcination：
Muffle furnace is risen to 600 DEG C, then step 2 gained sample is positioned on one piece of smooth ceramic wafer, then
It is sent into Muffle furnace with hawkbill, after calcining 1h, sample is taken out from 600 DEG C of Muffle furnace, is cooled down at room temperature；
(4) spin coating liquid is prepared：
Mixing 3.5mL glacial acetic acid obtains spin coating liquid with 1.5mL ethyl alcohol；
(5) spin-coating method handles alpha-ferric oxide light anode：
Alpha-ferric oxide film obtained by step (3) is fixed on sol evenning machine turntable, 30 μ L drops of spin coating liquid obtained by step (4) are taken
In thin film center, setting condition is that 3000rpm continues 30s after 1000rpm continues 10s.Gained sample is dried in Muffle furnace,
100 DEG C of lasting 1h, obtain alpha-ferric oxide light anode.The light anode structure does not have hole storage layer.
Comparative example 2
A kind of preparation method of light anode, includes the following steps：
(1) prepare conductive substrates：
By 2cm × 2.5cm sizes cutting FTO (SnO of doping fluorine2Transparent conducting glass), successively isopropanol, acetone,
Each ultrasound 15min, is then dried up with nitrogen in ethyl alcohol.Clean FTO conducting surfaces top about 0.5cm is covered with high temperature gummed tape,
The back side is all covered with high temperature gummed tape, is vertically placed in 50mL water heating kettles, and high temperature gummed tape is used in combination to fix its position；
(2) growth of β-FeOOH films：
By 0.2703g FeCl3·6H2O and 0.1420g Na2SO420mL is dissolved in three times in water, and 0.3mL TiCl are added4It is molten
(formula is 0.11mL TiCl to liquid4+ 10mL ethyl alcohol), obtain mixed solution；Then the mixed solution of preparation is poured into and has been placed with
It in the water heating kettle of FTO, is put in baking oven after tight encapsulation, setting temperature is 120 DEG C, continues 4h；It waits for throwing off base after reaction
High temperature gummed tape on bottom is used in combination water flushing three times, then uses N2Drying；
(3) β-FeOOH films are made it be converted into alpha-ferric oxide film by high-temperature calcination：
Muffle furnace is risen to 600 DEG C, then step 2 gained sample is positioned on one piece of smooth ceramic wafer, then
It is sent into Muffle furnace with hawkbill, after calcining 1h, sample is taken out from 600 DEG C of Muffle furnace, is cooled down at room temperature；
(4) electrodeposition process prepares molybdenum trioxide/alpha-ferric oxide compound light anode：
Molybdenum trioxide is hole storage layer commonly used in the prior art.5mmol/L sodium molybdate solutions are configured as electrolyte,
Use three-electrode system.Using Ag/AgCl electrodes as reference electrode, Pt pieces are used as to electrode, with alpha-ferric oxide obtained by step (3)
Film is working electrode.Application -0.6V biass continue 60s, with after-applied 0V biass, continue 60s, for a cycle.It holds in total
20 cycles of row.Then by working electrode rinse dry up, then in Muffle furnace 350 DEG C calcining 2 hours to get to molybdenum trioxide/
Alpha-ferric oxide compound light anode.
Performance test：
(1) hole storage volume is tested：
Using the electrochemical impedance spectroscopy of three-electrode system test light anode composite structure, hold to calculate the storage of its hole
Amount, specially：
Using Ag/AgCl electrodes as reference electrode, Pt pieces are used as to electrode, are answered with prepared in embodiment or comparative example
Object light anode is closed as working electrode；Using xenon lamp as light source, and AM1.5 optical filters are installed, light anode is adjusted when test to light
The distance in source makes to be 100mW/cm by force by irradiation2；Using 1mol/L NaOH solutions as electrolyte, electrochemical impedance spectroscopy is tested.If
It is 0.1Hz~100kHz, amplitude 5mV to set frequency range.Go out the interface of electrode-electric solution liquid with ZsimDemo software the Fitting Calculations
Capacitance.
Fig. 3 gives embodiment 1, the test result of embodiment 5 and comparative example 1.With unmodified alpha-ferric oxide light anode
(comparative example 1) is compared, and two Co base oxides/alpha-ferric oxide compound light anode (embodiment 1 and embodiment 5) are all shown more
The interface capacitance value of high electrode-electric solution liquid, shows CoO and Co3O4All have hole storage effect.And it can be by selecting not
The purpose of adjusting hole storage volume can be realized with the cobalt base oxide of valence state.Wherein CoO/ alpha-ferric oxides compound light anode
(embodiment 5) compares Co3O4/ alpha-ferric oxide compound light anode (embodiment 1) shows the interface electricity of higher electrode-electric solution liquid
Capacitance illustrates CoO ratios Co3O4With higher hole storage volume.
(2) photoelectrochemical behaviour of three-electrode system test light anode composite structure is used, specially：
Using Ag/AgCl electrodes as reference electrode, Pt pieces are used as to electrode, are answered with prepared in embodiment or comparative example
Object light anode is closed as working electrode；Using xenon lamp as light source, and AM1.5 optical filters are installed, light anode is adjusted when test to light
The distance in source makes to be 100mW/cm by force by irradiation2；Using 1mol/L NaOH solutions as electrolyte, test linear sweep voltammetry is bent
Line；Scanning range is 0.5 to 1.6V vs.RHE (voltage value relative to reversible hydrogen electrode), and it is 20mV/s to sweep speed.With 1.23V
Photoelectric current size under vs.RHE compares the performance of optoelectronic pole, and photoelectric current shows that more greatly performance is higher.
The performance test results are shown in Table 1：
Table 1
Experiment shows MoO3(comparative example 2) dissolves rapidly in alkaline solution, and stability is bad, and Co base oxides are (real
Apply example) it has good stability in alkaline solution.Have more preferably since alpha-ferric oxide compares in an acidic solution in alkaline solution
Performance and stability, therefore, when using alpha-ferric oxide as light-absorbing semiconductor, Co base oxides can be used as suitable hole storage
Layer.In addition, Co as can be seen from Table 13O4Effect is better than CoO, and Co3O4Optimal EDS maps density be 1~2 μ g/cm2。
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of hole accumulation layer for photoanode surface, which is characterized in that the hole accumulation layer is received for cobalt base oxide
Rice grain layer.
2. hole accumulation layer as described in claim 1, which is characterized in that in the hole accumulation layer, point of cobalt base oxide
Cloth density is 0.5~2 μ g/cm2；
Preferably, the cobalt base oxide includes cobaltosic oxide or cobalt black；
Preferably, when the cobalt base oxide is cobaltosic oxide, the distribution density in the accumulation layer of hole is 1~2 μ g/
cm2；
Preferably, when the cobalt base oxide is cobalt black, 0.5~0.6 μ g/ of distribution density in the accumulation layer of hole
cm2；
Preferably, the grain size of the cobalt base oxide nano particle is 3~6nm；
Preferably, the semiconductor light absorbent in the light anode is alpha-ferric oxide film；
Preferably, when the semiconductor light absorbent is alpha-ferric oxide film, the hole accumulation layer is received for cobaltosic oxide
Rice grain layer.
3. a kind of light anode composite construction, which is characterized in that the light anode includes electrically conducting transparent substrate, is grown on described transparent
Semiconductor light absorbent in conductive substrates, and it is covered in the hole accumulation layer on semiconductor light absorbent surface, the hole
Accumulation layer is the hole accumulation layer as claimed in claim 1 or 2 for photoanode surface.
4. light anode composite construction as claimed in claim 3, which is characterized in that the electrically conducting transparent substrate includes FTO transparent
Electro-conductive glass or transparent electro-conductive glass.
5. a kind of preparation method of light anode composite construction as described in claim 3 or 4, which is characterized in that the method packet
Include following steps：
(1) β-FeOOH films are grown in the precalculated position of electrically conducting transparent substrate by hydro-thermal reaction, precalculated position is obtained after calcining
Growth has the electrically conducting transparent substrate of alpha-ferric oxide film；
(2) cobalt base oxide nano particle is prepared, and is dispersed in solvent and prepares cobalt base oxide nanoparticulate dispersion；
(3) the cobalt base oxide nanoparticulate dispersion is coated to alpha-ferric oxide film surface, light is obtained after removing solvent
Anode composite structure.
6. preparation method as claimed in claim 5, which is characterized in that step (1) is described " by hydro-thermal reaction in electrically conducting transparent
β-FeOOH films are grown in substrate " the specific steps are：
The precalculated position of electrically conducting transparent substrate is exposed in the aqueous solution containing molysite and sodium salt by (1a), and titanium source dispersion is added dropwise
Liquid carries out hydro-thermal reaction by mixed solution under closed environment, and obtaining precalculated position growth has transparent the leading of β-FeOOH films
Electric substrate；
Preferably, the molysite includes trivalent iron salt, preferably ferric trichloride or trinitro- iron, a concentration of 0.05~0.15mol/L；
Preferably, the sodium salt includes sodium nitrate or sodium sulphate；
Preferably, in the aqueous solution containing molysite and sodium salt, a concentration of 0.05~0.2mol/L of sodium salt；
Preferably, the titanium source includes titanium tetrachloride；
Preferably, the dispersant of the titanium source dispersion liquid includes ethyl alcohol；
Preferably, titanium atom number accounts for the 1%~5% of the sum of iron atom and titanium atom number in the mixed solution；
Preferably, the temperature of the hydro-thermal reaction is 110~130 DEG C, and the time is 3.5~4.5h；It is preferred that the hydro-thermal reaction
Temperature is 120 DEG C, time 4h；
Preferably, the exposure chamber in the precalculated position is to cover non-predetermined position by high temperature gummed tape to realize the sudden and violent of precalculated position
Dew；
Preferably, the temperature of step (1) described calcining is 550~800 DEG C, and the time is 10min~120min；It is preferred that the temperature calcined
Degree is 600 DEG C, time 60min.
7. such as preparation method described in claim 5 or 6, which is characterized in that the preparation of " the cobalt base oxide nano particle "
Method is specially：
The dispersion in organic solvent of cobalt salt is carried out hydro-thermal reaction by (2a), obtains hydro-thermal reaction product；By hydro-thermal reaction product from
Cobalt base oxide nano particle is obtained after the heart, washing, drying；
Preferably, the cobalt salt includes divalent cobalt, preferably cobalt acetate or acetylacetone cobalt；
Preferably, when the cobalt salt is cobalt acetate, the organic solvent of the dispersion in organic solvent of the cobalt salt is ethyl alcohol, described
Ammonium hydroxide is also added in dispersion liquid, the hydrothermal temperature is 100~150 DEG C, and the reaction time is 2.5~3.5h；
It is further preferred that when the cobalt salt is cobalt acetate, the preparation method of the reaction system is：Cobalt acetate is dissolved in second
In alcohol, ammonium hydroxide is added under stirring condition, is kept stirring 10min；
Preferably, when the cobalt salt is acetylacetone cobalt, the hydrothermal temperature is 180~200 DEG C, the reaction time 12
~20h；
Preferably, the rotating speed of the centrifugation is 7000~9000rpm, preferably 8000rpm；
Preferably, the solvent of the cleaning is ethyl alcohol；
Preferably, the dispersant of step (2) the cobalt base oxide nanoparticulate dispersion is ethyl alcohol and/or acetic acid, preferably second
The mixed solvent of alcohol and acetic acid, further preferred volume ratio are 3:7 ethyl alcohol and the mixed solvent of acetic acid；
Preferably, in step (2) the cobalt base oxide nanoparticulate dispersion, the dispersion concentration of cobalt base oxide nano particle
For 0.1~2mg/mL.
8. the preparation method as described in one of claim 5~7, which is characterized in that the mode of the coating includes spin coating, drop
Arbitrary a kind or at least two kinds of of combination in Tu, dip-coating, it is preferably spun on；
Preferably, the step of spin coating is：30 μ L cobalt base oxide nanoparticulate dispersions are added dropwise to center of turntable, with
After the rotating speed of 800~1200rpm rotates 8~10s, then with 18~23s of rotating speed rotation of 2500~3500rpm；
Preferably, the method for removing solvent includes drying, and 0.8~1.2h is dried preferably at 95~105 DEG C.
9. a kind of application of compound light anode as described in claim 3 or 4, which is characterized in that the compound light anode
Water is decomposed for optical electro-chemistry.
10. a kind of device of photochemical catalyzing, which is characterized in that the working electrode of described device is described in claim 3 or 4
Compound light anode.
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| CN109675637A (en) * | 2018-12-19 | 2019-04-26 | 天津理工大学 | A kind of α-ferric oxide film preparation method of ferrous salt modification |
| CN110302785A (en) * | 2019-06-10 | 2019-10-08 | 广东工业大学 | A kind of unformed cobalt oxide/di-iron trioxide composite photo-catalyst and its preparation method and application |
| CN112547083A (en) * | 2019-09-25 | 2021-03-26 | 湘潭大学 | Method for improving photoelectric property of metal oxide semiconductor electrode material through different-phase cobalt oxide load |
| CN112547083B (en) * | 2019-09-25 | 2023-09-15 | 湘潭大学 | Method for improving photoelectric performance of tungsten trioxide photo-anode through cobalt monoxide loading of different phases |
| US11408084B2 (en) | 2020-01-09 | 2022-08-09 | King Fahd University Of Petroleum And Minerals | Thin film electrode containing nanostructured cobalt oxide for water splitting |
| CN111663140A (en) * | 2020-05-14 | 2020-09-15 | 中山大学 | Preparation of double-layer energy storage type photoelectric anode and application thereof in metal cathode protection |
| CN111663140B (en) * | 2020-05-14 | 2021-03-19 | 中山大学 | Preparation of double-layer energy storage type photoelectric anode and application thereof in metal cathode protection |
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