CN106378136B - The ferric oxide film and its preparation method and application of superthin layer iron titanate modification - Google Patents
The ferric oxide film and its preparation method and application of superthin layer iron titanate modification Download PDFInfo
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- CN106378136B CN106378136B CN201610679515.8A CN201610679515A CN106378136B CN 106378136 B CN106378136 B CN 106378136B CN 201610679515 A CN201610679515 A CN 201610679515A CN 106378136 B CN106378136 B CN 106378136B
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- 238000012986 modification Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000004048 modification Effects 0.000 title description 5
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 title description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title description 3
- 229910003079 TiO5 Inorganic materials 0.000 claims abstract description 102
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 238000004070 electrodeposition Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims abstract description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910052603 melanterite Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- 238000003303 reheating Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 230000005622 photoelectricity Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 151
- 239000010408 film Substances 0.000 description 103
- 239000010410 layer Substances 0.000 description 37
- 239000012528 membrane Substances 0.000 description 10
- 229940021013 electrolyte solution Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910002593 Fe-Ti Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- -1 acids Ester Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
Abstract
The invention discloses a kind of superthin layer Fe2TiO5Modified alpha-Fe2O3Film and its preparation method and application, the superthin layer Fe2TiO5Thickness be 5-15nm, be to be obtained by sintering reaction by Fe films and titanium colloidal sol, concrete scheme is：0.8ml butyl titanates are instilled in 60ml absolute ethyl alcohols first, is stirred until homogeneous, obtains titanium colloidal sol, slowly stretched into the Fe films that cathodic electrodeposition prepares in titanium colloidal sol using pulling machine, 2~5min are stood, to control Fe2TiO5Thickness range be 5-15nm, after be heat-treated up to superthin layer Fe through sintering2TiO5α-the Fe of modification2O3Film.Superthin layer α-Fe of the present invention2O3/Fe2TiO5Film has good visible absorption performance, good stability, high photoelectric efficiency and charge transfer effciency, can be widely applied to photocatalysis, photoelectrocatalysis decomposes in the fields such as water and photocatalysis wastewater fuel cell, manufacture.
Description
Technical field
The present invention relates to a kind of thin-film materials, and in particular to a kind of ferric oxide film of superthin layer iron titanate modification and
Preparation method and application, belong to technical field of nano material.
Technical background
Di-iron trioxide (α-Fe2O3) due to lower band-gap energy (2.1-2.2eV), and its is at low cost, nontoxic, steady
It is qualitative higher, to the promising catalysis material as moderns' concern.But α-Fe2O3Electric conductivity and short with difference
Hole transport distance, thus cause light induced electron and hole-recombination serious, seriously affect the performance that film is used as electrode.This
Outside, due to α-Fe2O3Conduction band be less than water reduction potential, therefore need higher applied voltage again to overcome this defect.Research
Persons take a variety of different methods to overcome these limitations, to improve α-Fe2O3The performance of film photoelectric electrode, including
Increase specific surface area by synthesizing the method control surface form of nanostructure and shortens carrier diffusion distance
(Angew.Chem.Int.Ed.2010,49,6405-6408), hetero-junctions is built with other catalysis materials to improve electronics
Hole separating effect (Chem.Soc.Rev., 2013,42,2568-2580), and into the doping of row metal or nonmetallic ion
And then improves lattice structure and promote electric conductivity (Sur.Science, 2012,258,2307-2311) etc..B.X.Zhou etc. utilizes the moon
Pole electrodeposition process directly deposits pure Fe films in conductive substrates, and then iron film is oxidized to α-Fe2O3Film, to promote α-Fe2O3
The ordered structure (J.Mater.Chem.A, 2015,3,4345-4353) of film, prepared by α-Fe2O3Film has preferable
Visible absorption performance and high light electrical efficiency.But α-the Fe that the above method obtains2O3Thin film stability is poor, service life
It is shorter.
Iron titanate (Fe2TiO5) Fe-Ti oxides are used as, have TiO2Excellent thermodynamic stability, P.S.Bassi etc.
It reports and utilizes Fe2O3With Fe2TiO5Constitute the research (Nano energy, 2016,22,310-318) of hetero-junctions, but due to
Fe2O3With Fe2TiO5Heterojunction structure in Fe2TiO5Layer thickness is larger, and thickness causes α-Fe up to more than 70 nm2O3What film generated
Photogenerated charge is still difficult to be diffused rapidly to electrode surface, thus can not be obviously improved α-Fe2O3The photoelectric properties of film.
Invention content
The present invention is directed to α-Fe2O3The deficiencies of poorly conductive, hole transport are difficult to detach apart from short, photogenerated charge, by
α-Fe2O3Film surface modifies one layer of ultra-thin Fe2TiO5Film has efficient photoelectricity treater catalytic performance and good stability to obtain
Visible light-responded Fe2TiO5α-the Fe of modification2O3Thin-film material.
To achieve the above object, the present invention is by the following technical programs to solve its technical problem：
A kind of superthin layer Fe2TiO5α-the Fe of modification2O3Film, which is characterized in that the superthin layer Fe2TiO5Thickness
For 5-15nm.
The present invention another technical solution be：
A kind of above-mentioned superthin layer Fe2TiO5α-the Fe of modification2O3The preparation method of film, superthin layer Fe2TiO5It is to pass through
Titanium colloidal sol is lifted in Fe film surfaces, it is then thermally treated, by Fe films and titanium colloidal sol by sintering reaction, directly obtain ultra-thin
Layer Fe2TiO5α-the Fe of modification2O3Film；Concrete scheme is：0.8ml butyl titanates are instilled in 60ml absolute ethyl alcohols, slightly
It is stirred until homogeneous, obtains titanium colloidal sol, the Fe films that then will be prepared using cathodic electrodeposition slowly stretch into preparation with pulling machine
In the good titanium colloidal sol, controls the Fe films and immerse the time of titanium colloidal sol for 2~5min, so that the superthin layer formed later
Fe2TiO5Then Fe films lifting is detached from the titanium colloidal sol by thickness by pulling machine again in 5~15nm ranges, when lifting rises
Speed and decrease speed are 300 μm/s, later by the Fe films of dipped titanium colloidal sol in 50 DEG C of dry 1h, then 500 DEG C of heat treatments
2h, subsequent 700 DEG C of reheating handle 10min to get the superthin layer Fe2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5)
Film.
The Fe films are prepared using cathodic electrodeposition, and the specific method is as follows：By 5g FeSO4·7H2O is dissolved in 150mL
In deionized water, the ammonium hydroxide of 30mL 27% is added and is vigorously stirred, electrolyte solution is obtained, with conductive substrates fluorine doped tin oxide
Electro-conductive glass is cathode, and platinized platinum is anode, the electro-deposition 30s under 2V voltages, and it is thin to obtain the Fe prepared using cathodic electrodeposition
Film.
The present invention another technical solution be：
A kind of superthin layer Fe2TiO5α-the Fe of modification2O3Film is fired in photocatalysis, photoelectrocatalysis and photocatalysis waste water
Expect the application in field of batteries.
Superthin layer Fe of the present invention2TiO5α-the Fe of modification2O3The preparation of film is by metal Fe films and titanium colloidal sol
Directly obtained by sintering reaction, have the characteristics that it is easy, time saving, efficient, with unmodified superthin layer Fe2TiO5α-Fe2O3It is thin
Membrane electrode and modification thick-layer Fe2TiO5α-Fe2O3Membrane electrode compares, and stability of the invention and photoelectric efficiency obtain
It is significantly promoted, this is because the present invention has following technical characterstic：
(1) superthin layer Fe2TiO5It is to be directly obtained by sintering reaction with titanium colloidal sol by pure metal Fe films, either
α-Fe2O3Or Fe2TiO5By sintering process self-assembling formation, therefore obtained film is relatively natural in lattice structure in it
Orderly, be conducive to the transmission of photogenerated charge；
(2)α-Fe2O3With Fe2TiO5Between there is level-density parameter relationship, see that Fig. 1, this level-density parameter relationship can expire
Sufficient electronics and the conduction in hole with detach, be conducive to overcome α-Fe2O3Hole transport is apart from short problem；
(3) since thickness only has the Fe of 5-15nm2TiO5The ultra-slim features of layer, are conducive to overcome α-Fe2O3Poorly conductive,
Hole transport is apart from short deficiency so that α-Fe2O3Photohole is easy to pass through Fe2TiO5Layer film is to electrode/electrolyte circle
Face is transmitted, and the compound of photogenerated charge is reduced；
(4) due to Fe2TiO5Excellent thermodynamic stability, to act as α-Fe2O3Protective layer effect, improve
α-Fe2O3/Fe2TiO5The stability of film.
Description of the drawings
Fig. 1 is α-Fe2O3With Fe2TiO5Level structure schematic diagram.
Fig. 2 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5The SEM and TEM of film scheme.
Wherein, A is unmodified α-Fe2O3Surface SEM schemes, and B is α-Fe2O3/Fe2TiO5Film surface SEM figures；C is not repair
Adorn α-Fe2O3Surface TEM schemes, and D is α-Fe2O3/Fe2TiO5Film surface TEM figures；E is α-Fe2O3/Fe2TiO5Film sections SEM
Figure.
Fig. 3 is α-Fe in embodiment 12O3/Fe2TiO5The xps energy spectrum figure of film.
α-the Fe as seen from Figure 32O3/Fe2TiO5Film free from admixture element (in figure in addition to containing Fe, O, Ti
C element derives from the CO of film surface absorption2)。
Fig. 4 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5The Raman spectrograms of film.
By α-Fe2O3/Fe2TiO5The Raman spectrograms of film can be seen that Fe2TiO5Characteristic peak positions appear in 660
And 792cm-1Place, shows α-Fe2O3/Fe2TiO5There are Fe in film2TiO5。
Fig. 5 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5The volt-ampere curve of film.
Fig. 6 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5Light of the film in the phosphate buffer of pH=7
Current versus time curve.
As can be seen from Figure, α-Fe2O3/Fe2TiO5Film light current stability is remarkably reinforced.
Fig. 7 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5Film in the KOH electrolyte solutions of 1M,
Photoelectric conversion efficiency (IPCE) curve under 1.23V (vs.RHE) bias and under each wavelength light irradiation.
Fig. 8 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5The AC impedance curve of film.
Fig. 9 is α-Fe in embodiment 12O3Film and α-Fe2O3/Fe2TiO5The modulated photocurrent collection of illustrative plates (IMPS) of film
Comparison diagram.
Figure 10 is Fe in embodiment 12TiO5α-the Fe of different modifying thickness2O3/Fe2TiO5The volt-ampere curve of film.
Figure 11 is the preparation method programme diagram of the present invention.
Specific implementation mode
The present invention is directed to α-Fe2O3The deficiencies of poorly conductive, hole transport are difficult to detach apart from short, photogenerated charge, by
α-Fe2O3Film surface modifies one layer of superthin layer Fe2TiO5Film obtains with efficient photoelectricity treater catalytic performance and well stablizes
The visible light-responded Fe of property2TiO5α-the Fe of modification2O3Thin-film material.
The superthin layer Fe2TiO5Be by Fe film surfaces lift titanium colloidal sol, it is then thermally treated, by Fe films
With titanium colloidal sol by sintering reaction, directly obtain.
The superthin layer Fe2TiO5Thickness be 5-15nm.
The superthin layer Fe2TiO5α-the Fe of modification2O3Film has good visible absorption performance, good steady
Qualitative, high photoelectric efficiency and charge transfer effciency can be widely applied to photocatalysis, photoelectrocatalysis and photocatalysis waste water fuel electricity
The technical fields such as pond.
It elaborates to the present invention with reference to embodiment and attached drawing, but the protection model of the present invention should not be limited with this
It encloses.
Embodiment 1
First cathodic electrodeposition is used to prepare Fe films：By 5g FeSO4·7H2O is dissolved in 150mL deionized waters, is added
The ammonium hydroxide of 30mL 27% simultaneously is vigorously stirred to obtain electrolyte solution, using conductive substrates fluorine doped tin oxide electro-conductive glass as cathode, platinum
Piece is anode, is inserted into the electrolyte solution, the electro-deposition 30s under 2V voltages, obtains the Fe films of cathodic electrodeposition preparation.
Then superthin layer Fe is prepared2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5) film：By four fourth of 0.8ml metatitanic acids
Ester instills in 60ml absolute ethyl alcohols, and gentle agitation obtains titanium colloidal sol to uniform, is then prepared above-mentioned using cathodic electrodeposition
Fe films, slowly stretched by pulling machine in the titanium colloidal sol prepared, control Fe films immerse titanium colloidal sol time be 3min, with
Control the superthin layer Fe formed later2TiO5Thickness is so lifted by pulling machine again in 10nm；Rise and fall speed is when lifting
300 μm/s, later by the Fe films of dipped titanium colloidal sol after 50 DEG C of dry 1h, 2h, subsequent 700 DEG C of reheating are heat-treated in 500 DEG C
10min is handled to get superthin layer Fe2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5) film.
α-the Fe2O3/Fe2TiO5Film light anode volt-ampere curve in the KOH electrode matter solution of 1M is tested, and photoelectric current is
1.71mA/cm2(1.23V vs RHE), stability 48 hours are constant, and photoelectric conversion efficiency reaches 32%.The thin-film material can be with
As photoelectrocatalysielectrode electrode in photoelectrocatalysis hydrogen manufacturing or degradation of organic substances and photocatalysis wastewater fuel cell, manufacture.
Illustrate the effect of embodiment 1 below with two reference examples.
Reference examples 1
α-Fe are prepared using publicly-owned preparation method (J.Mater.Chem.A, 2015,3,4345-4353)2O3Membrane electrode
(unmodified α-Fe2O3Film), concrete scheme is as follows：By 5g FeSO4·7H2O is dissolved in 150mL deionized waters, is added
The ammonium hydroxide of 30mL 27% simultaneously is vigorously stirred to obtain electrolyte solution, using conductive substrates fluorine doped tin oxide electro-conductive glass as cathode, platinum
Piece is anode, and the electro-deposition 30s under 2V voltages, cathode surface deposits to obtain Fe films, with deionized water rinse Fe films, and
50 DEG C or so dry 1h are heat-treated 2h in 500 DEG C to Fe films, are obtained not after natural cooling later in air atmosphere
α-the Fe of modification2O3Membrane electrode.
As a contrast, in the case where 1 other conditions of embodiment are constant, with unmodified α-Fe2O3Membrane electrode substitutes α-
Fe2O3/Fe2TiO5Film light anode tests volt-ampere curve, photoelectric current 0.68mA/cm in the KOH electrode matter solution of 1M2
(1.23Vvs RHE), only Fe in embodiment 12TiO5α-the Fe of modification2O3The photoelectric current 40% (see Fig. 5) of film, and do not repair
α-the Fe of decorations2O3Membrane electrode stability is poor, and initial stage decays more (see Fig. 6).At photoelectric conversion efficiency (IPCE) (see Fig. 7)
On, α-Fe2O3The IPCE of film is only 1 α-Fe of embodiment2O3/Fe2TiO5IPCE 31% (350nm).It is surveyed in AC impedance
In terms of examination, unmodified α-Fe2O3The impedance of film is obviously significantly higher than α-Fe2O3/Fe2TiO5(see Fig. 8), illustrates embodiment
α-Fe in 12O3/Fe2TiO5Electric conductivity is improved significantly.Fig. 9 gives unmodified α-Fe2O3In film and embodiment 1
α-Fe2O3/Fe2TiO5The comparison diagram of the modulated photocurrent collection of illustrative plates (IMPS) of film.Curve A is 1 α-Fe of embodiment in figure2O3/
Fe2TiO5The IMPS test curves of film, curve minimum point respective frequencies are 53Hz, when the average mobility of corresponding light induced electron
Between be 3.004ms；Curve B is unmodified α-Fe2O3Membrane electrode IMPS test curves, curve minimum point respective frequencies are
The average mobility time of 33Hz, corresponding light induced electron are 4.822ms.This shows unmodified α-Fe2O3Photoproduction current-carrying in film
The migration rate of son is significantly lower than α-Fe in embodiment 12O3/Fe2TiO5The migration rate of photo-generated carrier.
Reference examples 2
Fe is prepared using the method for embodiment 12TiO5Modify the Fe that layer thickness is 30nm2TiO5α-the Fe of modification2O3Film,
It is different from 1 place of embodiment：Fe films immerse titanium colloidal sol 3 times, and the corresponding process that lifts is 3 times, thus Fe2TiO5Modification
Layer thickness is the Fe of 30nm2TiO5α-the Fe of modification2O3Membrane electrode.
As a contrast, in the case where 1 other conditions of embodiment are constant, with Fe2TiO5It is 30nm's to modify layer thickness
Fe2TiO5α-the Fe of modification2O3Fe in membrane electrode alternate embodiment 12TiO5Modify the superthin layer α-Fe that layer thickness is 10nm2O3/
Fe2TiO5Photo-anode film is tested, photoelectric current 0.71mA/cm in the KOH electrode matter solution of 1M2(1.23V vs RHE),
Its photoelectric current is only 41% (see Figure 10) than embodiment 1, and the above results show Fe2TiO5In the case of modification layer thickness is thicker,
Fe cannot be obviously improved2TiO5α-the Fe of modification2O3The photoelectric properties of membrane electrode.
Fig. 2-Figure 10 gives α-Fe2O3α-the Fe of film, different modifying thickness2O3/Fe2TiO5Film and the present embodiment 1
α-the Fe of preparation2O3/Fe2TiO5The comparison of the performance of film.
Embodiment 2
First cathodic electrodeposition is used to prepare Fe films：By 5g FeSO4·7H2O is dissolved in 150mL deionized waters, is added
The ammonium hydroxide of 30mL 27% simultaneously is vigorously stirred to obtain electrolyte solution, using conductive substrates fluorine doped tin oxide electro-conductive glass as cathode, platinum
Piece is anode, is inserted into the electrolyte solution, the electro-deposition 30s under 2V voltages, obtains the Fe films of cathodic electrodeposition preparation.So
After prepare superthin layer Fe2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5) film：0.8ml butyl titanates are instilled into 60ml
In absolute ethyl alcohol, gentle agitation obtains titanium colloidal sol to uniform, the Fe films that then will be prepared using cathodic electrodeposition, by carrying
Machine drawing is slowly stretched into the titanium colloidal sol prepared, and the time that control Fe films immerse titanium colloidal sol is 2min, to be formed after control
Superthin layer Fe2TiO5Thickness is so lifted by pulling machine again in 5nm or so, and lifting rise and fall speed is 300 μm/s, later
By the Fe films of dipped titanium colloidal sol after 50 DEG C of dry 1h, 2h is heat-treated in 500 DEG C, subsequent 700 DEG C of reheating handle 10min, i.e.,
Obtain Fe2TiO5The superthin layer Fe that thickness is about 5nm2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5) film.α-the Fe2O3/
Fe2TiO5Light anode is tested in the KOH solution of 1M, photoelectric current 1.2mA/cm2(1.23V vsRHE) is that reference examples 1 are not repaiied
Adorn α-Fe2O31.8 times of film electrode photoelectric stream.
Embodiment 3
First cathodic electrodeposition is used to prepare Fe films：By 5g FeSO4·7H2O is dissolved in 150mL deionized waters, is added
The ammonium hydroxide of 30mL 27% simultaneously is vigorously stirred to obtain electrolyte solution, using conductive substrates fluorine doped tin oxide electro-conductive glass as cathode, platinum
Piece is anode, is inserted into the electrolyte solution, the electro-deposition 30s under 2V voltages, obtains the Fe films of cathodic electrodeposition preparation.So
After prepare superthin layer Fe2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5) film：0.8ml butyl titanates are instilled into 60ml
In absolute ethyl alcohol, gentle agitation obtains titanium colloidal sol to uniform, the Fe films that then will be prepared using cathodic electrodeposition, by carrying
Machine drawing is slowly stretched into the titanium colloidal sol prepared, and the time that control Fe films immerse titanium colloidal sol is 5min, to be formed after control
Superthin layer Fe2TiO5Thickness is so lifted by pulling machine again in 15nm or so, and lifting rise and fall speed is 300 μm/s, it
Afterwards by the Fe films of dipped titanium colloidal sol after 50 DEG C of dry 1h, 2h is heat-treated in 500 DEG C, subsequent 700 DEG C of reheating handle 10min,
Up to Fe2TiO5The superthin layer Fe that thickness is about 15nm2TiO5α-the Fe of modification2O3(α-Fe2O3/Fe2TiO5) film.The α-
Fe2O3/Fe2TiO5Light anode is tested in the KOH solution of 1M, photoelectric current 1.1mA/cm2(1.23V vsRHE) is reference examples 1
Unmodified α-Fe2O31.6 times of film electrode photoelectric stream.
Claims (3)
1. a kind of superthin layer Fe2TiO5α-the Fe of modification2O3The preparation method of film, which is characterized in that the superthin layer
Fe2TiO5Thickness be 5-15nm, be by Fe film surfaces lift titanium colloidal sol, it is then thermally treated, it is molten by Fe films and titanium
Glue directly obtains superthin layer Fe by sintering reaction2TiO5α-the Fe of modification2O3Film；Concrete scheme is：By 0.8ml metatitanic acids four
Butyl ester instills in 60ml absolute ethyl alcohols, and gentle agitation obtains titanium colloidal sol to uniform, then will be prepared using cathodic electrodeposition
Fe films are slowly stretched into pulling machine in the titanium colloidal sol prepared, control the Fe films immerse titanium colloidal sol time be 2~
5min, so that the superthin layer Fe formed later2TiO5Then thickness is again lifted the Fe films by pulling machine in 5~15nm ranges
It is detached from the titanium colloidal sol, the rate of climb and decrease speed are 300 μm/s when lifting, and the Fe films of dipped titanium colloidal sol exist later
50 DEG C of dry 1h, then 500 DEG C of heat treatment 2h, subsequent 700 DEG C of reheating handle 10min to get the superthin layer Fe2TiO5Modification
α-Fe2O3Film.
2. superthin layer Fe according to claim 12TiO5α-the Fe of modification2O3The preparation method of film, which is characterized in that institute
It states Fe films to prepare using cathodic electrodeposition, the specific method is as follows：By 5g FeSO4·7H2O is dissolved in 150mL deionized waters,
The ammonium hydroxide that 30mL mass fractions are 27% is added and is vigorously stirred, obtains electrolyte solution, is led with conductive substrates fluorine doped tin oxide
Electric glass is cathode, and platinized platinum is anode, the electro-deposition 30s under 2V voltages, obtains the Fe films prepared using cathodic electrodeposition.
3. superthin layer Fe described in a kind of claim 12TiO5α-the Fe of modification2O3The preparation method of film is urged in photocatalysis, photoelectricity
Change and the application in photocatalysis wastewater fuel cell, manufacture field.
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| CN1164198A (en) * | 1994-11-16 | 1997-11-05 | 东陶机器株式会社 | Photocatalytic functional material and method of production thereof |
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| CN101143357A (en) * | 2007-07-13 | 2008-03-19 | 清华大学 | Nanocrystalline film and its low temperature preparing method |
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| CN1164198A (en) * | 1994-11-16 | 1997-11-05 | 东陶机器株式会社 | Photocatalytic functional material and method of production thereof |
| CN1467023A (en) * | 2002-07-09 | 2004-01-14 | 中国科学院广州能源研究所 | Photocatalyst film having light activity visible basal body and method for preparing the same |
| CN101143357A (en) * | 2007-07-13 | 2008-03-19 | 清华大学 | Nanocrystalline film and its low temperature preparing method |
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| "Enhanced charge separation through ALD-Modified Fe2O3/Fe2TiO5 nanorod heterojunction for photoelectrochemical water oxidation";Chengcheng Li et al;《Small》;20160519;第12卷(第25期);第1-8页 * |
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