CN104478227A - Preparation method of hydrogen phosphate ion modified alpha-phase ferric oxide film - Google Patents

Preparation method of hydrogen phosphate ion modified alpha-phase ferric oxide film Download PDF

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Publication number
CN104478227A
CN104478227A CN201410730497.2A CN201410730497A CN104478227A CN 104478227 A CN104478227 A CN 104478227A CN 201410730497 A CN201410730497 A CN 201410730497A CN 104478227 A CN104478227 A CN 104478227A
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preparation
conductive glass
film
ferric oxide
phosphoric acid
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CN201410730497.2A
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CN104478227B (en
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薛松
刘侃
武全萍
王红艳
孙喆
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Tianjin University of Technology
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Tianjin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/217—FeOx, CoOx, NiOx

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a preparation method of a hydrogen phosphate ion modified alpha-phase ferric oxide film. The preparation method comprises the following steps: (1) cleaning and drying substrate FTO (Fluorine-doped Tin Oxide) conductive glass for later use; (2) immersing the FTO conductive glass in a mixed aqueous solution of phosphate and iron salt and placing in a sealed reactor, reacting in an oven of 80-150 DEG C for 5-10 hours, cooling to room temperature, opening the reactor and taking the FTO conductive glass out; and (3) calcining the FTO conductive glass in a muffle furnace at 400-800 DEG C for 10-60 minutes to obtain the hydrogen phosphate ion modified alpha-phase ferric oxide film. The preparation method has the advantages of simple preparation process, cheap raw materials, easiness in operation, low production cost, cleanness and no pollution; the prepared alpha-phase ferric oxide film has the advantages of good charge separation capability and catalytic oxygen evolution activity, the recombination probability of electron-hole pairs is decreased, the property of nanometer ferric oxide for photoelectric catalytic decomposition of water is improved and the preparation method is expected to be used in the field of industrial production.

Description

The preparation method of the ɑ phase ferricoxide film that a kind of phosphoric acid hydrogen radical ion is modified
Technical field
The present invention relates to the preparation method of ferric oxide film, especially relate to the preparation method of the ɑ phase ferricoxide film that a kind of phosphoric acid hydrogen radical ion is modified.
Background technology
Hydrogen Energy is the clean energy that a kind of application potential is very large.1972, Japanese professor Fujishima proposed nano titanium oxide (TiO first 2) there is the ability of catalytic decomposition water hydrogen manufacturing under ultra violet lamp, which results in the great interest of scientific circles to photocatalytic hydrogen production by water decomposition.At present, utilize sun power, the photochemical catalyzing technology using semiconductor nano material as photocatalyst becomes one of hydrogen production process of most magnetism.
Take titanium dioxide as the Conventional nano photocatalyst material of representative, due to its band gap length, low to solar energy utilization ratio, seriously hinder the practical application of photocatalyst material.For this reason, people constantly explore to develop and have visible light-responded novel photocatalysis material.ɑ phase Fe 2o 3the band gap width of semiconductor material is narrow, and have very strong visible absorption efficiency, visible-range can reach 590nm, meanwhile, and its stable chemical nature, rich content.Therefore, ɑ phase ferricoxide semiconductor material is considered to a kind of desirable photocatalyst material, has become a focus to the research of its photocatalysis performance.But there is hole transport apart from shortcomings such as short, electron-hole recombination probability are high in nanometer ɑ phase ferricoxide, limits the efficiency of its photocatalytic water.Improved the electroconductibility of nanometer ɑ phase ferricoxide film by elements such as Doped with Titanium, tin, silicon, be convenient to hole transport, improve photoelectric current.It is pass through Al that another kind is improved one's methods 2o 3, Ga 2o 3, In 2o 3, the metal oxides such as Co-Pi or phosphoric acid salt are modified ferric oxide surface, to change surface state or to improve catalysis traffic order regularity.Adopt inexpensive phosphate anion to modify ferric oxide film surface, also can significantly improve photoelectric current, increase phototranstormation efficiency.Therefore, prepare the ɑ phase ferricoxide film of the phosphate modified of high catalytic activity with inexpensive raw material, promote charge separation, improve and put oxygen catalytic capability, thus make it have better photocatalytic water performance, in clean energy field, there is very important Research Significance.
Summary of the invention
The object of the invention is for the low problem of ferric oxide film catalysis traffic order regularity, the preparation method of the ɑ phase ferricoxide film that a kind of phosphoric acid hydrogen radical ion is modified is proposed, this preparation method adopts water heat transfer, Sodium phosphate dibasic is joined in ferric chloride Solution, when iron(ic) chloride hydro-thermal reaction generates intermediate FeOOH, its surface is containing a large amount of hydroxyl-OH, be easy to react with phosphoric acid hydrogen radical ion, the ferric oxide film surface obtained through roasting again has abundant phosphate anion, promote the charge separation on ferric oxide film surface, to improve photoelectric current and photocatalytic water puts oxygen ability.
Technical scheme of the present invention:
Phosphoric acid hydrogen radical ion modify ɑ phase ferricoxide film a preparation method, step is as follows:
1) matrix FTO conductive glass is used liquid detergent, deionized water, ethanol, chloroform ultrasonic cleaning successively, for subsequent use after nitrogen drying;
2) by phosphoric acid salt and molysite soluble in water, obtain mixed solution, FTO conductive glass be immersed in this mixed solution, be positioned in the reactor of sealing, in the baking oven of 80-150 DEG C, react 5-10 hour, after being cooled to room temperature, open reactor, take out FTO conductive glass;
3) by above-mentioned FTO conductive glass in retort furnace in 400-800 DEG C of roasting 10-60 minute, obtain phosphate anion modify a phase ferricoxide film.
Described phosphoric acid salt is sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassiumphosphate, potassium hydrogen phosphate or potassium primary phosphate; Molysite is iron nitrate, iron(ic) chloride or ferric sulfate; In mixed solution, phosphatic concentration is 0.0015 mol/L, and the concentration of molysite is 0.15 mol/L.
Advantage of the present invention is: 1) preparation technology is simple, raw material is cheap, processing ease, preparation cost are low and cleanliness without any pollution; 2) Sodium phosphate dibasic and iron(ic) chloride are together added in mixed solution, more easily form the electronegative phosphoric acid hydrogen radical ion of one deck on ferric oxide film surface, there is good charge separation ability and catalysis traffic order regularity; 3) a phase ferricoxide film obtained is thinner, and thickness is 30-80nm, reduces electronics and hole to the probability of compound, improves the photoelectrocatalysis water of decomposition performance of nanometer ferric oxide, be expected to be applied at field of industrial production.
Accompanying drawing explanation
Fig. 1 is the photoelectricity flow graph of obtained a phase ferricoxide film.
In figure: curve (1) is the photoelectric current of a phase ferricoxide film prepared by embodiment 1, curve (4) is the dark current of a phase ferricoxide film prepared by embodiment 1; Curve (2) is the photoelectric current of the film of phosphoric acid hydrogen radical ion modification prepared by comparative example 2, and curve (5) is the dark current of the film of phosphoric acid hydrogen radical ion modification prepared by comparative example 2; Curve (3) is the photoelectric current of a phase ferricoxide film of phosphoric acid hydrogen radical ion immersion prepared by comparative example 3, and curve (6) is the dark current of a phase ferricoxide film of phosphoric acid hydrogen radical ion immersion prepared by comparative example 3.
Embodiment
Embodiment one:
Phosphoric acid hydrogen radical ion modify ɑ phase ferricoxide film a preparation method, step is as follows:
1) FTO conductive glass is cut into the square of 10 × 30mm, uses liquid detergent, deionized water, ethanol, chloroform ultrasonic cleaning matrix FT0 conductive glass successively, for subsequent use after nitrogen drying; ;
2) by 0.0537g Na 2hPO 412H 2o and 2.433g FERRIC CHLORIDE ANHYDROUS is dissolved in 100mL water, obtains mixed solution, i.e. iron trichloride and Na in mixed solution 2hPO 4concentration be respectively 0.15 mol/L and 0.0015 mol/L, FTO conductive glass is immersed in this mixed solution, is positioned in the reactor of sealing, react 6 hours in the baking oven of 100 DEG C, after being cooled to room temperature, open reactor, take out FTO conductive glass;
3) small beaker of submergence FTO conductive glass is whole is put in reactor inner bag, by reactor good seal, in 700 DEG C of roastings 20 minutes in retort furnace, obtains a phase ferricoxide film that phosphate anion is modified.
Comparative example 2:
The preparation process of this comparative example is substantially the same manner as Example 1, and difference is: do not add Na 2hPO 4and obtained film.
Comparative example 3:
The preparation process of this comparative example is substantially the same manner as Example 1, and difference is: do not add Na 2hPO 4and obtained a phase ferricoxide film, then this film is immersed in the Na of 0.5M 2hPO 4solution 1 hour, takes out rear deionized water rinsing, is placed in retort furnace and sinters 20 minutes in 700 DEG C, the nanometer a phase ferricoxide film that obtained phosphoric acid hydrogen radical ion soaks.
The analysis of the photoelectricity flow graph of obtained a phase ferricoxide film:
With the nanometer ɑ phase ferricoxide film of preparation for working electrode, platinized platinum is to electrode, Ag/AgCl electrode is reference electrode, and test by electrochemical workstation linear sweep voltammetry the photoelectrocatalysis water of decomposition performance that we prepare film, sweep voltage scope is-0.3 ~ 1.0V vs Ag/AgCl.Ionogen is the potassium phosphate solution (PH=7) of 0.1M, and light source is that (light intensity is 100 mW cm to simulated solar irradiation -2).This nanometer a phase ferricoxide film has larger photoelectric current to occur under photoelectric action.
Fig. 1 is the photoelectricity flow graph of obtained a phase ferricoxide film.In figure: curve (1) is the photoelectric current of a phase ferricoxide film of phosphoric acid hydrogen radical ion modification prepared by embodiment 1, curve (4) is the dark current of a phase ferricoxide film of phosphoric acid hydrogen radical ion modification prepared by embodiment 1; Curve (2) is the photoelectric current of a phase ferricoxide film prepared by comparative example 2, and curve (5) is the dark current of a phase ferricoxide film prepared by comparative example 2; Curve (3) is the photoelectric current of a phase ferricoxide film of phosphoric acid hydrogen radical ion immersion prepared by comparative example 3, and curve (6) is the dark current of a phase ferricoxide film of phosphoric acid hydrogen radical ion immersion prepared by comparative example 3.
Show in figure: by modifying or immersion process, the photoelectric current of a phase ferricoxide film containing phosphate anion of preparation is all strong than the photoelectric current in curve (2), illustrates that phosphate anion has the effect obviously promoting photoelectric current at a phase ferricoxide film surface; Curve (1) is compared with curve (3), shows that the film that the film light current ratio that phosphate anion is modified is soaked is strong, illustrates that phosphoric acid salt and iron(ic) chloride together add reaction, and the photoelectric current of a phase ferricoxide film of the phosphoric acid hydrogen radical ion modification of preparation is best.The enhancing of photoelectric current, the raising of the photoelectrocatalysis water of decomposition performance of display ferric oxide film.

Claims (2)

1. phosphoric acid hydrogen radical ion modify ɑ phase ferricoxide film a preparation method, it is characterized in that step is as follows:
1) matrix FTO conductive glass is used liquid detergent, deionized water, ethanol, chloroform ultrasonic cleaning successively, for subsequent use after nitrogen drying;
2) by phosphoric acid salt and molysite soluble in water, obtain mixed solution, FTO conductive glass be immersed in this mixed solution, be positioned in the reactor of sealing, in the baking oven of 80-150 DEG C, react 5-10 hour, after being cooled to room temperature, open reactor, take out FTO conductive glass;
3) by above-mentioned FTO conductive glass in retort furnace in 400-800 DEG C of roasting 10-60 minute, obtain phosphate anion modify a phase ferricoxide film.
2. according to claim 1 phosphoric acid hydrogen radical ion modify ɑ phase ferricoxide film preparation method, it is characterized in that: described phosphoric acid salt is sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassiumphosphate, potassium hydrogen phosphate or potassium primary phosphate; Molysite is iron nitrate, iron(ic) chloride or ferric sulfate; In mixed solution, phosphatic concentration is 0.0015 mol/L, and the concentration of molysite is 0.15 mol/L.
CN201410730497.2A 2014-12-05 2014-12-05 The preparation method of α-ferric oxide film that a kind of phosphoric acid hydrogen radical ion is modified Expired - Fee Related CN104478227B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109731615A (en) * 2018-12-19 2019-05-10 天津理工大学 A kind of α-ferric oxide film preparation method of Zn-MOF modification
CN109879608A (en) * 2019-04-10 2019-06-14 广州大学 A method of corrosion recrystallization method prepares polyhedron FeOOH film
CN111647908A (en) * 2020-07-01 2020-09-11 淮阴工学院 Method for improving photoelectric response of iron oxide nanorod array photoelectric anode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004210573A (en) * 2002-12-27 2004-07-29 Mitsuboshi Belting Ltd Manufacturing method of glass with iron oxide film
CN101314524A (en) * 2008-07-04 2008-12-03 北京工业大学 Method for preparing alpha type ferric oxide film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004210573A (en) * 2002-12-27 2004-07-29 Mitsuboshi Belting Ltd Manufacturing method of glass with iron oxide film
CN101314524A (en) * 2008-07-04 2008-12-03 北京工业大学 Method for preparing alpha type ferric oxide film

Non-Patent Citations (3)

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JAE YOUNG KIM,ET AL.: "A stable and efficient hematite photoanode in a neutral electrolyte for solar water splitting:towards stability engineering", 《ADVANCED ENERGY MATERIALS》 *
LI FU,ET AL.: "Cobalt phosphate group modified hematite nanorod array as photoanode for efficient solar water splitting", 《ELECTROCHIMICA ACTA》 *
孟庆强等: "磷酸修饰对纳米Fe2O3热稳定性及光催化性能的影响", 《高等学校化学学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109731615A (en) * 2018-12-19 2019-05-10 天津理工大学 A kind of α-ferric oxide film preparation method of Zn-MOF modification
CN109879608A (en) * 2019-04-10 2019-06-14 广州大学 A method of corrosion recrystallization method prepares polyhedron FeOOH film
CN111647908A (en) * 2020-07-01 2020-09-11 淮阴工学院 Method for improving photoelectric response of iron oxide nanorod array photoelectric anode

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