CN104773959B - One kind prepares BiVO using biomimetic method4The method of film - Google Patents

One kind prepares BiVO using biomimetic method4The method of film Download PDF

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CN104773959B
CN104773959B CN201510149628.2A CN201510149628A CN104773959B CN 104773959 B CN104773959 B CN 104773959B CN 201510149628 A CN201510149628 A CN 201510149628A CN 104773959 B CN104773959 B CN 104773959B
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film
bivo
substrate
precursor liquid
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CN104773959A (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 present invention provides a kind of using biomimetic method preparation BiVO4The method of film, five water bismuth nitrates and vanadic acid ammonia are soluble in water, pH value is adjusted with dust technology, with boric acid as accelerator, precursor liquid is made, substrate is carried out into functionalization under ultraviolet light, substrate surface is formed hydroxyl layer, then the substrate of functionalization is suspended in precursor liquid surface, by hydroxyl layer identification inorganic matter molecule in substrate surface heterogeneous nucleation, reverse induced growth prepares noncrystalline membrane, and noncrystalline membrane dries the BiVO that after annealing prepares crystallization4Film.Present invention process is simple, and experiment condition requirement is relatively low, and technical process is easy to control.The method is the successful Application to liquid phase self-assembling technique, and the method for the present invention is applied into BiVO4The preparation of film, has broad application prospects in photocatalysis field.

Description

One kind prepares BiVO using biomimetic method4The method of film
Technical field
The invention belongs to field of functional materials, and in particular to one kind prepares BiVO using biomimetic method4The method of film.
Background technology
Photocatalitic Technique of Semiconductor is a focus for developing emerging research field in recent decades, due to photocatalysis skill Art has the advantages that the process is simple for itself not polluting, completing, directly can utilize sun radiant, thus in the depollution of environment Widely paid close attention in field.In recent years, BiVO4As a class novel semi-conductor catalysis material, because its band gap is narrower (about 2.4eV), wavelength response range expands to 520nm or so, photochemical properties are stable, redox ability is strong, nontoxic, inexpensive etc. Advantage, as the focus of visible light photocatalysis research field.
At present, for BiVO4The preparation method of film mainly has sol-gel process, physical vaporous deposition etc..Colloidal sol- Gel method low production cost, it is simple to operate, be suitably adapted for material of different shapes, large area uniform film can be prepared and film Purity is high.But the method can produce substantial amounts of debirs, and technique is cumbersome, slightly deal with improperly, film and substrate just occurs With reference to it is insecure, cracking the problems such as.Physical vaporous deposition has that technical process is simple, it is few, environment-friendly to pollute small, consumptive material, The features such as film has even compact and is firmly combined with matrix, but it is poor there is also process repeatability, it is costly The problems such as.Chemical liquid deposition method is a kind of wet chemical method, and it does not need expensive device, is suitable to large area and prepares film, It is widely used in synthesizing various functions material, and achieves huge success.
Self-assembled monolayer (self-assembled monolayers, SAMs) technology be one be referred from it is bionic New film technique.The orderly unimolecule hydroxyl adsorption layer spontaneously formed on substrate interface is irradiated by short wave ultraviolet light. Because most of hydrocarbons have stronger absorbability to the ultraviolet light of 184.9nm wavelength, 184.9nm wavelength it is ultraviolet Line can be by the O in air2(oxygen) becomes O3(ozone) and elemental oxygen, in turn, ultraviolet light of the ozone to 184.9nm wavelength Also there is strong absorption, ozone is decomposed into elemental oxygen and oxygen again, wherein the elemental oxygen for decomposing generation is extremely active, it The carbon and hydrocarbon of residual resolve into volatilizable gas (CO after substrate surface can be caused to clean2And H2O), it is thoroughly clear Except carbon and organic pollution on substrate surface, at the same time, the hydroxyl free radical of free state, these hydroxyl free radical meetings are produced Substrate surface is adsorbed in, substrate surface is adsorbed one layer of hydroxyl, hydroxyl adsorption layer.The hydroxyl adsorption layer of formation is spontaneous in atmosphere Be firmly adsorbed on the ultra-thin hydroxyl film formed on substrate by chemical bond, thus it spontaneously formed with original position, bonding it is high Degree ordered arrangement, defect is few, adhesion is strong, in " crystalline state " the features such as.Because hydroxyl adsorption layer preparation method is simple, film forming effect Really good, stability is strong, thicknesses of layers is ultra-thin, therefore just start in terms of heterogeneous nucleation induction inorganic material film preparation should With.
The content of the invention
It is an object of the invention to provide one kind BiVO is prepared using biomimetic method4The method of film, the inventive method experiment Condition requirement is relatively low, is referred from bionic liquid phase self-assembling technique, and BiVO is prepared using interface hydroxyl layer heterogeneous nucleation4It is thin Film.
To achieve the above object, the technical solution adopted by the present invention is：
One kind prepares BiVO using biomimetic method4The method of film, comprises the following steps：
1) configuration of precursor liquid：
Xiang Shuizhong adds NH4VO3, stir to clarify, dust technology is subsequently adding, stir, add Bi (NO3)3· 5H2O, stirs to clarify at room temperature, is eventually adding boric acid, stirs, and obtains precursor liquid；Bi (NO in precursor liquid3)3·5H2O's Concentration is 0.010~0.012mol/L, NH4VO3Concentration be 0.010~0.012mol/L, HNO3Concentration for 0.415~ 0.420mol/L, the concentration of boric acid is 0.010~0.012mol/L；
2) functionalization of substrate：
Irradiation under ultraviolet light will be placed in after substrate washes clean, substrate surface is formed hydroxyl layer, obtain surface-functionalized Substrate；
3) deposition of film：
The one side of functional substrate is suspended in precursor liquid surface, 10~12h is deposited at 70~80 DEG C, using substrate surface [(BiVO in the molecular recognition function absorption precursor liquid of hydroxyl layer3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and then anneals, and 300~550 DEG C insulation 100~140min, obtain the BiVO of crystallization4Film.
The step 1) middle addition NH4VO3In after stir to clarify needed for time be 20~40min.
The step 1) in add dust technology after stir needed for time be 5~15min.
The step 1) middle addition Bi (NO3)3·5H2Time needed for being stirred to clarify after O is 40~80min.
The step 1) in add boric acid after stir needed for time be 5~15min.
The substrate is FTO electro-conductive glass, ITO electro-conductive glass, glass slide or Si substrates.
The step 2) in washing be that substrate is sequentially placed into 5~15min of supersound washing in water, acetone, absolute ethyl alcohol.
The step 2) in substrate is placed in 30~50min is irradiated under the ultraviolet light of 184.9nm.
The BiVO of described crystallization4The crystal formation of film is compound crystal formation, the list 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, its pattern are the ball that the block and irregular sheet of hexahedron is agglomerated into Body.
Relative to prior art, the invention has the advantages that：
The utilization biomimetic method that the present invention is provided prepares BiVO4The method of film is a kind of new preparation BiVO4The side of film Method, the method is referred from bionic liquid phase self-assembling technique, and BiVO is prepared using interface hydroxyl layer heterogeneous nucleation4Film. The method makes precursor liquid first, HNO in precursor liquid3It is inhibitor, suppresses Bi (NO3)3Form BiONO3, boric acid is promotion Agent, promotes NH4VO3Form NH4 +And VO3 -, HNO3Make to form [(BiVO in precursor liquid with boric acid collective effect3)2+NO3 -]+, then Surface-functionalized modified, the orderly layer of the hydroxyl with hydrophilicity of formation is carried out to substrate using ultraviolet light, will be changed Property after the functionalized surface of substrate contacted with precursor liquid, inorganic matter molecule is recognized by hydroxyl (- OH) layer, it is different in substrate surface Phase nucleation, reverse adsorption induction, liquid deposition has been obtained [(BiVO3)2+NO3 -]+OH-Precursor thin film, then by under different temperatures The BiVO for preparing by annealing crystallization4Film.The present invention combines the advantage of liquid phase self assembly, obtained by reverse adsorption BiVO4Film is conducive to improving BiVO than more loose4The photocatalysis performance of film.Process is simple of the invention, experiment condition will Ask relatively low.The method is the successful Application to liquid phase self-assembling technique, and the method for the present invention is applied into BiVO4The system of film It is standby, had broad application prospects in photocatalysis field.
Brief description of the drawings
Fig. 1 is BiVO prepared by the present invention4The XRD spectra of film, wherein a~f are respectively 1~embodiment of embodiment 6 and make The BiVO for obtaining4The XRD of film；
Fig. 2 is BiVO prepared by the embodiment of the present invention 34The SEM figures of film.
Specific embodiment
The present invention is described in further detail with reference to embodiment and accompanying drawing.
Embodiment 1
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 30min is subsequently adding dust technology to clarifying, stirring 10min to uniform, Add Bi (NO3)3·5H2O, stirs 60min to clarifying completely at room temperature, is eventually adding boric acid, and 10min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.012mol/L, NH4VO3Concentration be 0.012mol/L, HNO3Concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L；
2) functionalization of substrate：
Glass slide substrate is sequentially placed into supersound washing 10min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 40min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11h is deposited at 75 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 120min is incubated at 300 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 2
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 30min is subsequently adding dust technology to clarifying, stirring 10min to uniform, Add Bi (NO3)3·5H2O, stirs 60min to clarifying completely at room temperature, is eventually adding boric acid, and 10min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.012mol/L, NH4VO3Concentration be 0.012mol/L, HNO3Concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L；
2) functionalization of substrate：
Glass slide substrate is sequentially placed into supersound washing 10min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 40min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11h is deposited at 75 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 120min is incubated at 350 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 3
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 30min is subsequently adding dust technology to clarifying, stirring 10min to uniform, Add Bi (NO3)3·5H2O, stirs 60min to clarifying completely at room temperature, is eventually adding boric acid, and 10min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.012mol/L, NH4VO3Concentration be 0.012mol/L, HNO3Concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L；
2) functionalization of substrate：
Glass slide substrate is sequentially placed into supersound washing 10min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 40min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11h is deposited at 75 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 120min is incubated at 400 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 4
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 30min is subsequently adding dust technology to clarifying, stirring 10min to uniform, Add Bi (NO3)3·5H2O, stirs 60min to clarifying completely at room temperature, is eventually adding boric acid, and 10min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.012mol/L, NH4VO3Concentration be 0.012mol/L, HNO3Concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L；
2) functionalization of substrate：
Glass slide substrate is sequentially placed into supersound washing 10min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 40min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11h is deposited at 75 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 120min is incubated at 450 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 5
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 30min is subsequently adding dust technology to clarifying, stirring 10min to uniform, Add Bi (NO3)3·5H2O, stirs 60min to clarifying completely at room temperature, is eventually adding boric acid, and 10min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.012mol/L, NH4VO3Concentration be 0.012mol/L, HNO3Concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L；
2) functionalization of substrate：
Glass slide substrate is sequentially placed into supersound washing 10min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 40min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11h is deposited at 75 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 120min is incubated at 500 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 6
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 30min is subsequently adding dust technology to clarifying, stirring 10min to uniform, Add Bi (NO3)3·5H2O, stirs 60min to clarifying completely at room temperature, is eventually adding boric acid, and 10min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.012mol/L, NH4VO3Concentration be 0.012mol/L, HNO3Concentration be 0.418mol/L, the concentration of boric acid is 0.012mol/L；
2) functionalization of substrate：
Glass slide substrate is sequentially placed into supersound washing 10min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 40min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11h is deposited at 75 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 120min is incubated at 550 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 7
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 20min is subsequently adding dust technology to clarifying, stirring 15min to uniform, Add Bi (NO3)3·5H2O, stirs 40min to clarifying completely at room temperature, is eventually adding boric acid, and 15min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.01mol/L, NH4VO3Concentration be 0.01mol/L, HNO3 Concentration be 0.415mol/L, the concentration of boric acid is 0.01mol/L；
2) functionalization of substrate：
FTO conducting glass substrates are sequentially placed into supersound washing 15min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 30min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 12h is deposited at 70 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 100min is incubated at 520 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 8
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 40min is subsequently adding dust technology to clarifying, stirring 5min to uniform, Add Bi (NO3)3·5H2O, stirs 80min to clarifying completely at room temperature, is eventually adding boric acid, and 5min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.011mol/L, NH4VO3Concentration be 0.011mol/L, HNO3Concentration be 0.42mol/L, the concentration of boric acid is 0.011mol/L；
2) functionalization of substrate：
ITO conducting glass substrates are sequentially placed into supersound washing 5min in deionized water, acetone, absolute ethyl alcohol, will be washed Substrate after clean irradiates 50min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains function of surface The substrate of change；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 10h is deposited at 80 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of basic unit3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 110min is incubated at 480 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 9
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 25min is subsequently adding dust technology to clarifying, stirring 12min to uniform, Add Bi (NO3)3·5H2O, stirs 50min to clarifying completely at room temperature, is eventually adding boric acid, and 12min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.0105mol/L, NH4VO3Concentration be 0.0105mol/L, HNO3Concentration be 0.416mol/L, the concentration of boric acid is 0.0105mol/L；
2) functionalization of substrate：
Si substrates are sequentially placed into supersound washing 12min in deionized water, acetone, absolute ethyl alcohol, after washes clean Substrate irradiates 35min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains surface-functionalized substrate；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 11.5h is deposited at 72 DEG C, using substrate surface [(BiVO in the molecular recognition function absorption precursor liquid of hydroxyl layer3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 130min is incubated at 420 DEG C, obtain the BiVO of crystallization4Film.
Embodiment 10
1) configuration of precursor liquid：
To adding NH in deionized water4VO3, stirring 35min is subsequently adding dust technology to clarifying, stirring 8min to uniform, Add Bi (NO3)3·5H2O, stirs 70min to clarifying completely at room temperature, is eventually adding boric acid, and 8min is to uniform for stirring, obtains Precursor liquid；Bi (NO wherein in precursor liquid3)3·5H2The concentration of O is 0.0115mol/L, NH4VO3Concentration be 0.0115mol/L, HNO3Concentration be 0.419mol/L, the concentration of boric acid is 0.0115mol/L；
2) functionalization of substrate：
Si substrates are sequentially placed into supersound washing 8min in deionized water, acetone, absolute ethyl alcohol, by the base after washes clean Plate irradiates 45min under being placed in the ultraviolet light of 184.9nm, substrate surface is formed hydroxyl layer, obtains surface-functionalized substrate；
3) deposition of film：
The one of functional substrate is faced down, precursor liquid surface is suspended in, 10.5h is deposited at 78 DEG C, using substrate surface [(BiVO in the molecular recognition function absorption precursor liquid of hydroxyl layer3)2+NO3 -]+, then heterogeneous nucleation composition is amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and is then placed in being annealed in Muffle furnace, And 140min is incubated at 320 DEG C, obtain the BiVO of crystallization4Film.
By BiVO obtained in embodiment 1 to embodiment 64Film carries out XRD tests, wherein a~f be respectively embodiment 1 to BiVO obtained in embodiment 64The XRD spectrum of film, as can be seen from Figure 1 embodiment 1, embodiment 3, embodiment 4 and implementation BiVO prepared by example 54Film is equal Tetragonal moral navajoite (JCPDSNo.14-0133) and the oblique navajoite (JCPDS of monoclinic phase No.14-0688) compound BiVO4Film, BiVO prepared by embodiment 24Film is the oblique navajoite of monoclinic phase (JCPDS No.14- 0688) BiVO4Film, BiVO prepared by embodiment 64Film is the BiVO of Tetragonal moral navajoite (JCPDS No.75-1867)4 Film.
Fig. 2 is BiVO obtained in the embodiment of the present invention 34The SEM figures of film, it can be seen that obtained BiVO4Film has two kinds The spheroid that the block and irregular sheet of different patterns, respectively hexahedron is agglomerated into.
One embodiment of the present invention is the foregoing is only, is not all of or unique implementation method, this area is common Any equivalent conversion that technical staff is taken technical solution of the present invention by reading description of the invention, is the present invention Claim covered.

Claims (6)

1. it is a kind of to prepare BiVO using biomimetic method4The method of film, it is characterised in that comprise the following steps：
1) configuration of precursor liquid：
Xiang Shuizhong adds NH4VO3, stir to clarify, dust technology is subsequently adding, stir, add Bi (NO3)3·5H2O, room Stirred to clarify under temperature, be eventually adding boric acid, 5~15min is to stirring for stirring, obtains precursor liquid；Bi (NO in precursor liquid3)3· 5H2The concentration of O is 0.010~0.012mol/L, NH4VO3Concentration be 0.010~0.012mol/L, HNO3Concentration be 0.415~0.420mol/L, the concentration of boric acid is 0.010~0.012mol/L；
2) functionalization of substrate：
Irradiation under ultraviolet light will be placed in after substrate washes clean, substrate surface is formed hydroxyl layer, obtain surface-functionalized base Plate；
3) deposition of film：
The one side of functional substrate is suspended in precursor liquid surface, 10~12h is deposited at 70~80 DEG C, using substrate surface hydroxyl [(BiVO in the molecular recognition function absorption precursor liquid of layer3)2+NO3 -]+, then heterogeneous nucleation constitute amorphous [(BiVO3 )2+NO3 -]+OH-Precursor thin film；
4) crystallization of film：
By amorphous [(BiVO3)2+NO3 -]+OH-Precursor thin film is dried at room temperature for, and then anneals, and in 300~550 DEG C of guarantors 100~140min of temperature, obtains the BiVO of crystallization4Film, the BiVO of crystallization therein4The crystal formation of film be Tetragonal moral navajoite and The oblique navajoite crystal formation of the compound crystal formation of the oblique navajoite of monoclinic phase, monoclinic phase or Tetragonal moral navajoite crystal formation, its pattern are block hexahedron The spheroid being agglomerated into irregular sheet.
2. utilization biomimetic method according to claim 1 prepares BiVO4The method of film, it is characterised in that：The step 1) in Add NH4VO3In after stir to clarify needed for time be 20~40min.
3. utilization biomimetic method according to claim 1 prepares BiVO4The method of film, it is characterised in that：The step 1) in The required time is stirred for 5~15min after adding dust technology.
4. utilization biomimetic method according to claim 1 prepares BiVO4The method of film, it is characterised in that：The step 1) in Add Bi (NO3)3·5H2Time needed for being stirred to clarify after O is 40~80min.
5. utilization biomimetic method according to claim 1 prepares BiVO4The method of film, it is characterised in that：The substrate is FTO electro-conductive glass, ITO electro-conductive glass or Si substrates.
6. utilization biomimetic method according to claim 1 prepares BiVO4The method of film, it is characterised in that：The step 2) in Substrate is placed in 30~50min of irradiation under the ultraviolet light of 184.9nm.
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