CN104773959A - Method for preparing BiVO4 film through biomimetic method - Google Patents

Method for preparing BiVO4 film through biomimetic method Download PDF

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CN104773959A
CN104773959A CN201510149628.2A CN201510149628A CN104773959A CN 104773959 A CN104773959 A CN 104773959A CN 201510149628 A CN201510149628 A CN 201510149628A CN 104773959 A CN104773959 A CN 104773959A
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film
bivo
substrate
precursor liquid
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CN104773959B (en
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谈国强
许驰
折辽娜
任慧君
夏傲
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a method for preparing a BiVO4 film through a biomimetic method. The method comprises the following steps: dissolving bismuth nitrate pentahydrate and ammonium vanadate into water to form a precursor solution, wherein the pH value is adjusted by dilute nitric acid and boric acid is used as an accelerant; functionalizing a base plate under the UV-irradiation so as to form a hydroxyl layer on the surface of the base plate, suspending the functionalized base plate over the surface of the precursor solution, identifying the heterogeneous nucleation of inorganic molecules on the surface of the base plate through the hydroxyl layer, performing reverse induced growth to prepare an amorphous film, drying the amorphous film, and annealing to prepare the crystallized BiVO4 film. The method is simple in process, low in experiment condition requirement and easy in technical process control. The method is a successful application of a liquid phase self-assembly technology, is applied to preparation of the BiVO4 film and has a wide application prospect in the photocatalytic field.

Description

One utilizes biomimetic method to prepare BiVO 4the method of film
Technical field
The invention belongs to field of functional materials, be specifically related to one and utilize biomimetic method to prepare BiVO 4the method of film.
Background technology
Photocatalitic Technique of Semiconductor is the focus developing emerging research field in recent decades, the technique do not pollute because photocatalysis technology has self, completed is simple, directly by advantages such as sunlight light source utilizations, thus can be paid close attention to widely in environmental purification field.In recent years, BiVO 4as a class novel semi-conductor photocatalyst material, because its band gap narrower (about 2.4eV), wavelength response range expand to the advantages such as about 520nm, photochemical properties is stable, redox ability is strong, nontoxic, inexpensive, becoming the focus of visible light photocatalysis research field.
At present, for BiVO 4the preparation method of film mainly contains sol-gel method, physical vaporous deposition etc.Sol-gel method production cost is low, simple to operate, can be suitable for difform material, can prepare large area uniform film and the purity of film is high.But this method can produce a large amount of organic waste, and technique is loaded down with trivial details, slightly deals with improperly, just there will be film and substrate in conjunction with problems such as insecure, be full of cracks.Physical vaporous deposition have technological process simple, pollute little, consumptive material is few, environmental friendliness, film have even compact and with matrix in conjunction with the feature such as firm, but the problem such as it is poor to there is also process repeatability, cost intensive.Chemical liquid deposition method is a kind of wet chemical method, and it does not need expensive device, is suitable for big area and prepares film, is widely used in synthesizing various functional materials, and achieves huge success.
Self-assembled monolayer (self-assembled monolayers, SAMs) technology is one and is referred from bionic novel film technique.By the orderly unit molecule hydroxyl adsorption layer of short wavelength UV photoirradiation spontaneous formation on substrate interface.Because the UV-light of most of hydrocarbon polymer to 184.9nm wavelength has stronger receptivity, the ultraviolet of 184.9nm wavelength can by the O in air 2(oxygen) becomes O 3(ozone) and atomic oxygen, conversely, ozone also has strong sorption to the UV-light of 184.9nm wavelength, ozone is decomposed into again atomic oxygen and oxygen, the atomic oxygen wherein decomposing generation is extremely active, and after it can make substrate surface clean, residual carbon becomes volatilizable gas (CO with hydrocarbons decompose 2and H 2o), thoroughly remove the carbon on substrate surface and organic pollutant, meanwhile, produce the hydroxyl free radical of free state, these hydroxyl free radicals can be adsorbed in substrate surface, make substrate surface adsorb one deck hydroxyl, hydroxyl adsorption layer.The hydroxyl adsorption layer formed spontaneously in atmosphere is adsorbed on the ultra-thin hydroxyl film that substrate is formed securely by chemical bond, therefore it has the spontaneous formation of original position, becomes the arrangement of key high-sequential, defect is few, bonding force is strong, be features such as " crystal forms ".Because hydroxyl adsorption layer preparation method is simple, film-formation result good, stability is strong, thicknesses of layers is ultra-thin, therefore in prepared by heterogeneous nucleation induction inorganic material film, just start application.
Summary of the invention
One is the object of the present invention is to provide to utilize biomimetic method to prepare BiVO 4the method of film, the inventive method requirement for experiment condition is lower, is referred from bionic liquid phase self-assembling technique, utilizes interface hydroxyl layer heterogeneous nucleation to prepare BiVO 4film.
For achieving the above object, the technical solution used in the present invention is:
One utilizes biomimetic method to prepare BiVO 4the method of film, comprises the following steps:
1) configuration of precursor liquid:
Xiang Shuizhong adds NH 4vO 3, stir to clarify, then add dust technology, stir, then add Bi (NO 3) 35H 2o, stirred at ambient temperature, to clarification, finally adds boric acid, stirs, obtain precursor liquid; Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.010 ~ 0.012mol/L, NH 4vO 3concentration be 0.010 ~ 0.012mol/L, HNO 3concentration be 0.415 ~ 0.420mol/L, the concentration of boric acid is 0.010 ~ 0.012mol/L;
2) functionalization of substrate:
Irradiate under substrate washes clean is placed on UV-light, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
The one side of functional substrate is suspended in precursor liquid surface, at 70 ~ 80 DEG C of deposition 10 ~ 12h, utilizes the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then anneals, and at 300 ~ 550 DEG C of insulation 100 ~ 140min, obtains the BiVO of crystallization 4film.
Described step 1) in add NH 4vO 3in after to stir to clarify the required time be 20 ~ 40min.
Described step 1) in add dust technology after required time that stirs be 5 ~ 15min.
Described step 1) in add Bi (NO 3) 35H 2stirring to clarify the required time after O is 40 ~ 80min.
Described step 1) in add boric acid after required time that stirs be 5 ~ 15min.
Described substrate is FTO conductive glass, ITO conductive glass, glass slide or Si substrate.
Described step 2) in washing be substrate is placed in successively water, acetone, dehydrated alcohol supersound washing 5 ~ 15min.
Described step 2) in substrate is placed in the UV-light of 184.9nm under irradiate 30 ~ 50min.
The BiVO of described crystallization 4the crystal formation of film is the compound crystal formation of Tetragonal moral navajoite and the oblique navajoite of monoclinic phase, the oblique navajoite crystal formation of monoclinic phase or Tetragonal moral navajoite crystal formation, and its pattern is the spheroid that the block and irregular sheet of hexahedron is agglomerated into.
Relative to prior art, the present invention has following beneficial effect:
The biomimetic method that utilizes provided by the invention prepares BiVO 4the method of film is a kind of novel preparation BiVO 4the method of film, the method is referred from bionic liquid phase self-assembling technique, utilizes interface hydroxyl layer heterogeneous nucleation to prepare BiVO 4film.First the method makes precursor liquid, HNO in precursor liquid 3for inhibitor, suppress Bi (NO 3) 3form BiONO 3, boric acid is promotor, promotes NH 4vO 3form NH 4 +and VO 3 -, HNO 3make to form [(BiVO in precursor liquid with boric acid acting in conjunction 3) 2+nO 3 -] +then UV-irradiation is utilized to carry out surface-functionalized modification to substrate, the orderly hydroxyl layer with hydrophilicity formed, the functionalized surface of modified substrate is contacted with precursor liquid, by hydroxyl (-OH) layer identification inorganics molecule, in substrate surface heterogeneous nucleation, reverse adsorption is induced, and liquid deposition has obtained [(BiVO 3) 2+nO 3 -] +oH -precursor thin film, then the BiVO preparing by annealing crystallization under differing temps 4film.The present invention in conjunction with the advantage of liquid phase self-assembly, by reverse adsorption, obtained BiVO 4film is more loose, is conducive to improving BiVO 4the photocatalysis performance of film.Technique of the present invention is simple, and requirement for experiment condition is lower.The method is the successful Application to liquid phase self-assembling technique, and method of the present invention is applied to BiVO 4the preparation of film, has broad application prospects in photocatalysis field.
Accompanying drawing explanation
Fig. 1 is BiVO prepared by the present invention 4the XRD spectra of film, wherein a ~ f is respectively the obtained BiVO of embodiment 1 ~ embodiment 6 4the XRD figure of film;
Fig. 2 is BiVO prepared by the embodiment of the present invention 3 4the SEM figure of film.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 30min to clarification, then add dust technology, stir 10min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 60min, to clarifying completely, finally add boric acid, stir 10min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.012mol/L, NH 4vO 3concentration be 0.012mol/L, HNO 3concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L;
2) functionalization of substrate:
Glass slide substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 10min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 40min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 75 DEG C of deposition 11h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 120min at 300 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 2
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 30min to clarification, then add dust technology, stir 10min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 60min, to clarifying completely, finally add boric acid, stir 10min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.012mol/L, NH 4vO 3concentration be 0.012mol/L, HNO 3concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L;
2) functionalization of substrate:
Glass slide substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 10min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 40min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 75 DEG C of deposition 11h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 120min at 350 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 3
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 30min to clarification, then add dust technology, stir 10min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 60min, to clarifying completely, finally add boric acid, stir 10min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.012mol/L, NH 4vO 3concentration be 0.012mol/L, HNO 3concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L;
2) functionalization of substrate:
Glass slide substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 10min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 40min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 75 DEG C of deposition 11h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 120min at 400 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 4
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 30min to clarification, then add dust technology, stir 10min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 60min, to clarifying completely, finally add boric acid, stir 10min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.012mol/L, NH 4vO 3concentration be 0.012mol/L, HNO 3concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L;
2) functionalization of substrate:
Glass slide substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 10min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 40min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 75 DEG C of deposition 11h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 120min at 450 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 5
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 30min to clarification, then add dust technology, stir 10min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 60min, to clarifying completely, finally add boric acid, stir 10min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.012mol/L, NH 4vO 3concentration be 0.012mol/L, HNO 3concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L;
2) functionalization of substrate:
Glass slide substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 10min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 40min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 75 DEG C of deposition 11h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 120min at 500 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 6
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 30min to clarification, then add dust technology, stir 10min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 60min, to clarifying completely, finally add boric acid, stir 10min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.012mol/L, NH 4vO 3concentration be 0.012mol/L, HNO 3concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L;
2) functionalization of substrate:
Glass slide substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 10min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 40min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 75 DEG C of deposition 11h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 120min at 550 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 7
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 20min to clarification, then add dust technology, stir 15min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 40min, to clarifying completely, finally add boric acid, stir 15min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.01mol/L, NH 4vO 3concentration be 0.01mol/L, HNO 3concentration be 0.415mol/L, the concentration of boric acid is 0.01mol/L;
2) functionalization of substrate:
FTO conducting glass substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 15min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 30min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 70 DEG C of deposition 12h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 100min at 520 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 8
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 40min to clarification, then add dust technology, stir 5min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 80min, to clarifying completely, finally add boric acid, stir 5min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.011mol/L, NH 4vO 3concentration be 0.011mol/L, HNO 3concentration be 0.42mol/L, the concentration of boric acid is 0.011mol/L;
2) functionalization of substrate:
ITO conducting glass substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 5min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 50min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 80 DEG C of deposition 10h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 110min at 480 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 9
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 25min to clarification, then add dust technology, stir 12min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 50min, to clarifying completely, finally add boric acid, stir 12min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.0105mol/L, NH 4vO 3concentration be 0.0105mol/L, HNO 3concentration be 0.416mol/L, the concentration of boric acid is 0.0105mol/L;
2) functionalization of substrate:
Si substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 12min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 35min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 72 DEG C of deposition 11.5h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 130min at 420 DEG C, obtains the BiVO of crystallization 4film.
Embodiment 10
1) configuration of precursor liquid:
NH is added in deionized water 4vO 3, stir 35min to clarification, then add dust technology, stir 8min extremely evenly, then add Bi (NO 3) 35H 2o, stirred at ambient temperature 70min, to clarifying completely, finally add boric acid, stir 8min to evenly, obtain precursor liquid; Wherein Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.0115mol/L, NH 4vO 3concentration be 0.0115mol/L, HNO 3concentration be 0.419mol/L, the concentration of boric acid is 0.0115mol/L;
2) functionalization of substrate:
Si substrate is placed in successively deionized water, acetone, dehydrated alcohol supersound washing 8min, under the substrate after washes clean being placed in the UV-light of 184.9nm, irradiates 45min, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
Face down one of functional substrate, be suspended in precursor liquid surface, at 78 DEG C of deposition 10.5h, utilize the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then puts into retort furnace and anneals, and is incubated 140min at 320 DEG C, obtains the BiVO of crystallization 4film.
By BiVO obtained for embodiment 1 to embodiment 6 4film carries out XRD test, and wherein a ~ f is respectively the obtained BiVO of embodiment 1 to embodiment 6 4the XRD figure spectrum of film, the BiVO of as can be seen from Figure 1 embodiment 1, embodiment 3, embodiment 4 and embodiment 5 preparation 4film is the BiVO of equal Tetragonal moral navajoite (JCPDSNo.14-0133) and the oblique navajoite of monoclinic phase (JCPDS No.14-0688) compound 4film, BiVO prepared by embodiment 2 4film is the BiVO of the oblique navajoite of monoclinic phase (JCPDS No.14-0688) 4film, BiVO prepared by embodiment 6 4film is the BiVO of Tetragonal moral navajoite (JCPDS No.75-1867) 4film.
Fig. 2 is the BiVO that the embodiment of the present invention 3 obtains 4the SEM figure of film, can find out obtained BiVO 4film has two kinds of different patterns, is respectively the spheroid that the block and irregular sheet of hexahedron is agglomerated into.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.

Claims (9)

1. one kind utilizes biomimetic method to prepare BiVO 4the method of film, is characterized in that, comprises the following steps:
1) configuration of precursor liquid:
Xiang Shuizhong adds NH 4vO 3, stir to clarify, then add dust technology, stir, then add Bi (NO 3) 35H 2o, stirred at ambient temperature, to clarification, finally adds boric acid, stirs, obtain precursor liquid; Bi (NO in precursor liquid 3) 35H 2the concentration of O is 0.010 ~ 0.012mol/L, NH 4vO 3concentration be 0.010 ~ 0.012mol/L, HNO 3concentration be 0.415 ~ 0.420mol/L, the concentration of boric acid is 0.010 ~ 0.012mol/L;
2) functionalization of substrate:
Irradiate under substrate washes clean is placed on UV-light, make substrate surface form hydroxyl layer, obtain surface-functionalized substrate;
3) deposition of film:
The one side of functional substrate is suspended in precursor liquid surface, at 70 ~ 80 DEG C of deposition 10 ~ 12h, utilizes the [(BiVO in the molecular recognition function absorption precursor liquid of substrate surface hydroxyl layer 3) 2+nO 3 -] +, the then amorphous [(BiVO of heterogeneous nucleation composition 3) 2+nO 3 -] +oH -precursor thin film;
4) crystallization of film:
By amorphous [(BiVO 3) 2+nO 3 -] +oH -precursor thin film is at room temperature dry, then anneals, and at 300 ~ 550 DEG C of insulation 100 ~ 140min, obtains the BiVO of crystallization 4film.
2. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described step 1) in add NH 4vO 3in after to stir to clarify the required time be 20 ~ 40min.
3. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described step 1) in add dust technology after required time that stirs be 5 ~ 15min.
4. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described step 1) in add Bi (NO 3) 35H 2stirring to clarify the required time after O is 40 ~ 80min.
5. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described step 1) in add boric acid after required time that stirs be 5 ~ 15min.
6. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described substrate is FTO conductive glass, ITO conductive glass, glass slide or Si substrate.
7. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described step 2) in washing be substrate is placed in successively water, acetone, dehydrated alcohol supersound washing 5 ~ 15min.
8. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: described step 2) in substrate is placed in the UV-light of 184.9nm under irradiate 30 ~ 50min.
9. the biomimetic method that utilizes according to claim 1 prepares BiVO 4the method of film, is characterized in that: the BiVO of described crystallization 4the crystal formation of film is the compound crystal formation of Tetragonal moral navajoite and the oblique navajoite of monoclinic phase, the oblique navajoite crystal formation of monoclinic phase or Tetragonal moral navajoite crystal formation, and its pattern is the spheroid that the block and irregular sheet of hexahedron is agglomerated into.
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* Cited by examiner, † Cited by third party
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CN105948530A (en) * 2016-04-25 2016-09-21 陕西科技大学 BiVO4 film with polyporous netted structure and preparation method thereof
CN106925256A (en) * 2017-03-30 2017-07-07 陕西科技大学 A kind of visible light-responded characteristic titanium oxide/pucherite hetero-junction thin-film and its preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101659520A (en) * 2009-09-17 2010-03-03 陕西科技大学 Method for preparing bismuth iron functional film on glass substrate by utilizing liquid-phase self-assembly method
CN102583568A (en) * 2012-02-16 2012-07-18 陕西科技大学 Method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment
CN102949991A (en) * 2012-11-09 2013-03-06 陕西科技大学 Method for preparing BiVO4 film with photocatalysis performance by using sol-gel method
WO2014136783A1 (en) * 2013-03-07 2014-09-12 学校法人東京理科大学 Bismuth-vanadate-laminate manufacturing method and bismuth-vanadate laminate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101659520A (en) * 2009-09-17 2010-03-03 陕西科技大学 Method for preparing bismuth iron functional film on glass substrate by utilizing liquid-phase self-assembly method
CN102583568A (en) * 2012-02-16 2012-07-18 陕西科技大学 Method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment
CN102949991A (en) * 2012-11-09 2013-03-06 陕西科技大学 Method for preparing BiVO4 film with photocatalysis performance by using sol-gel method
WO2014136783A1 (en) * 2013-03-07 2014-09-12 学校法人東京理科大学 Bismuth-vanadate-laminate manufacturing method and bismuth-vanadate laminate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948530A (en) * 2016-04-25 2016-09-21 陕西科技大学 BiVO4 film with polyporous netted structure and preparation method thereof
CN105948530B (en) * 2016-04-25 2019-02-22 陕西科技大学 A kind of porous network structure BiVO4Film and preparation method thereof
CN106925256A (en) * 2017-03-30 2017-07-07 陕西科技大学 A kind of visible light-responded characteristic titanium oxide/pucherite hetero-junction thin-film and its preparation method and application
CN106925256B (en) * 2017-03-30 2019-05-10 陕西科技大学 A kind of visible light-responded characteristic titanium oxide/pucherite hetero-junction thin-film and its preparation method and application

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