CN104192907A - Preparation method of gamma-bismuth molybdate nanotubes - Google Patents
Preparation method of gamma-bismuth molybdate nanotubes Download PDFInfo
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Abstract
The invention relates to a preparation method of gamma-bismuth molybdate nanotubes. The method comprises the following steps: adding citric acid into anhydrous ethanol and water, sealing, and completely dissolving; adding ammonium molybdate, bismuth nitrate pentahydrate and an acid solution to obtain a bismuth molybdate solution; adding the bismuth molybdate solution into the anhydrous ethanol and water, stirring uniformly, adding polyvinylpyrrolidone. completely dissolving, and adding an acid solution to obtain a bismuth molybdate sol; carrying out electrostatic spinning on the bismuth molybdate sol to obtain bismuth molybdate threads; and finally, drying the bismuth molybdate threads, heating to 200-800 DEG C, and calcining for 60-180 minutes while keeping the temperature. The gamma-bismuth molybdate nanotubes prepared by electrostatic spinning can better degrade methyl orange, methylene blue and the like as compared with the flaky gamma-bismuth molybdate prepared by a sol-gel process. The preparation method has the advantages of simple steps, low cost and controllable nanotube diameter.
Description
Technical field
The preparation method who the present invention relates to a kind of γ-bismuth molybdate nanotube, belongs to technical field of inorganic nonmetallic materials.
Background technology
Bismuth molybdate is a kind of compound with laminate structure, and its chemical general formula is Bi
2o
3nMoO
3, wherein n=3,2,1, corresponds respectively to α-Bi
2mo
3o
12, β-Bi
2mo
2o
9, γ-Bi
2moO
6.γ-bismuth molybdate (γ-Bi
2moO
6) be the defective fluorite type structure compound of tool, there is octahedral MoO
4 2-layer and (Bi
2o
2)
2+the laminate structure that sheath is built, Bi atomic shell is positioned at MoO
6in the interlayer of octahedral layer, energy gap is 2.70eV, has energy band structure that responding to visible light excites and high photo-generated carrier movability, is a kind of good novel photocatalysis material.
γ-Bi at present
2moO
6main preparation methods have solid phase method (referring to: Chinese patent literature CN102345163A), hydrothermal method is (referring to Chinese Journal of Inorganic Chemistry, 2009,25 (3), 512), solvent-thermal method is (referring to Journal of Nanoscience and Nanotechnology, 2011,10,4168), sol-gel method is (referring to Acta PhySico-Chimica Sinica 2007,23 (11); 1671) etc., these method synthesizeds be γ-Bi
2moO
6powder body material, particle diameter is large, and specific surface area is little, and the separation difficulty of powdered material in solution reaction also limited its use range.
Nanotube-shaped material is due to its unique physical and chemical performance and have potential using value in fields such as catalysis, medicine, nanoelectronic, opto-electronic devices and caused showing great attention to of investigators, and scientists is being explored the preparation method of hollow structure nanofiber always.Zhang etc. have introduced employing electrostatic spinning technique and have prepared γ-Bi in conjunction with solvent thermal process
2moO
6micron tube (referring to: Journal of Hazardous Materials2012,225,166), its preparation process is roughly and first adopts electrostatic spinning technique to prepare polyacrylonitrile to enter fiber, then using it as template, prepare the conjugated fibre of the polyacrylonitrile/γ-bismuth molybdate (PAN/BMO) of nucleocapsid structure with solvent-thermal method, and then sintering is removed PAN masterplate and is obtained γ-Bi
2moO
6micron tube.Due in the time that the core of PAN is removed in calcining to PAN/BMO, can produce toxic substance; And prepared γ-Bi
2moO
6be micron order tubular construction, do not possess nano effect.At present, to hollow structure γ-Bi
2moO
6the preparation of nanotube there is not yet relevant report, therefore seek to design one simply, γ-Bi fast
2moO
6the preparation method of nanotube, has potential theoretical significance and useful application and is worth.
The method is compared with the traditional template synthesis method of preparing tubular structure nanofiber, and step is simpler, and a step just can be prepared.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of γ-bismuth molybdate nanotube.
Term explanation
Spinning receiving range: electrostatic spinning syringe needle is to the distance of receiving trap.
Technical scheme of the present invention is as follows:
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) citric acid is joined in the mixing solutions of dehydrated alcohol and water, sealing, is stirred to and dissolves completely; Add ammonium molybdate and five water Bismuth trinitrates, stir 30-300min; Adding concentration is the acid solution of 30-50wt%, is stirred to solution clarification, obtains bismuth molybdate solution;
Described dehydrated alcohol and the volume ratio of water are (5-30): (5-30), it is (0.1-5) that described citric acid adds quality and the ratio of the volume of dehydrated alcohol: (5-30) g/ml, the mol ratio of described ammonium molybdate and five water Bismuth trinitrates is (0.01-8): (0.1-8), the molar weight of described ammonium molybdate is (0.01-8) with the ratio of the volume of dehydrated alcohol: (5-30) mol/L; Described acid solution and the volume ratio of dehydrated alcohol are (0.5-5): (5-30), described acid solution is hydrochloric acid, acetic acid or nitric acid;
(2) bismuth molybdate solution step (1) being made joins in the mixing solutions of dehydrated alcohol and water, stir, add polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add again the acid solution described in step (1), obtain bismuth molybdate colloidal sol;
The volume ratio of described bismuth molybdate solution, dehydrated alcohol and water is (0.5-5): (2-18): (1-10), it is (0.6-4) that described polyvinylpyrrolidone adds quality and the ratio of the volume of bismuth molybdate solution: (0.5-5) g/ml; The volume ratio of described acid solution and bismuth molybdate solution is (0.1-3.5): (0.5-5);
(3) bismuth molybdate colloidal sol step (2) being made is in 15-30kV voltage, and humidity is 15-50%, carries out electrostatic spinning under room temperature condition, and spinning receiving range is 15-25cm, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning step (3) being made is in 60-80 DEG C of dry 12-36h, then is warming up to 200-800 DEG C with the temperature rise rate of 0.5-5 DEG C/min, and insulation calcining 60-180min, to obtain final product.
According to the present invention, preferably, in step (1), described dehydrated alcohol and the volume ratio of water are (8-12): (8-12), it is (2-2.5) that described citric acid adds quality and the ratio of the volume of dehydrated alcohol: (8-12) g/ml, the mol ratio of described ammonium molybdate and five water Bismuth trinitrates is (0.3-0.5): (4.5-5.5), the molar weight of described ammonium molybdate is (0.3-0.4) with the ratio of the volume of dehydrated alcohol: (8-12) mol/L; Described acid solution and the volume ratio of dehydrated alcohol are (2-3): (8-12).
According to the present invention, preferably, in step (2), the volume ratio of described bismuth molybdate solution, dehydrated alcohol and water is (2-3): (8-12): (2-5), it is (0.6-1.2) that described polyvinylpyrrolidone adds quality and the ratio of the volume of bismuth molybdate solution: (2-3) g/ml; The volume ratio of described acid solution and bismuth molybdate solution is (0.1-1.0): (2-3).
According to the present invention, preferred, in step (3), electrostatic spinning voltage is 18-25kV voltage; Humidity is 20-35%.
According to the present invention, in step (3), electrostatic spinning can carry out with existing installation; Preferably, use the plastic injector with stainless steel syringe needle that bismuth molybdate colloidal sol is sprayed onto to electrostatic spinning in dash receiver, ejection speed is 0.001-0.002mm/s; Distance (being spinning receiving range) between syringe needle and the dash receiver of syringe is preferably 18-22cm, more preferably 20cm; The preferred 0.3-0.9mm of syringe needle internal diameter.
According to the present invention, preferred, in step (4), drying temperature is 50-80 DEG C; Temperature rise rate is 1-3 DEG C/min, and calcining temperature is 300-700 DEG C, insulation 90-150min.
The present invention adopts sol-gel method and electrostatic spinning technique to combine and prepares bismuth molybdate spinning, after bismuth molybdate spinning is dried, obtain bismuth molybdate gelled fibre, gelled fibre diameter 0.5-2 μ m, and after calcining, nanotube diameter is 200-800nm.
γ-bismuth molybdate that the present invention makes is sodium mitron structure, and diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
The bismuth molybdate nanotube that the present invention prepares can be used for the photocatalytic oxidation degradation of rhodamine B, tropeolin-D, methylene blue.
Beneficial effect of the present invention:
1, sheet γ-bismuth molybdate that γ-bismuth molybdate nanotube that prepared by electrostatic spinning of the present invention is prepared than sol-gel method can better degrade tropeolin-D, methylene blue etc.
2, preparation method's step of the present invention is simple, with low cost, and the diameter of nanotube is easy to control.
3,, in preparation method of the present invention, preferably material matching makes nanofiber be easy to form; Preferably spinning condition makes nanofiber diameter even; Preferably calcination condition has been avoided the fracture of nanotube and the doping of a large amount of particulate materials.
4, γ-bismuth molybdate nanotube that prepared by the present invention, compared with the γ-bismuth molybdate of other forms, has larger specific surface area and stronger adsorptive power, can improve photocatalysis performance and the photoelectric transformation efficiency of γ-bismuth molybdate.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram (XRD) of γ-bismuth molybdate nanotube of making of the embodiment of the present invention 3.
Fig. 2 is scanning electron microscope (SEM) figure of γ-bismuth molybdate nanotube of making of the embodiment of the present invention 4.
Fig. 3 is scanning electron microscope (SEM) figure of γ-bismuth molybdate nanotube of making of the embodiment of the present invention 1, and the illustration in Fig. 3 upper left corner is transmission electron microscope (TEM) figure.
Fig. 4 is scanning electron microscope (SEM) figure of γ-bismuth molybdate nanotube of making of the embodiment of the present invention 2.
Fig. 5 is the diffuse reflection spectrum of γ-bismuth molybdate nanotube of making of the embodiment of the present invention 1, and the illustration in Fig. 5 upper right corner is that photoabsorption coefficient (α hv) is to energy (hv) variation relation figure, according to formula α hv=A (hv-E
g)
1/2, α is photoabsorption coefficient, and v is light frequency, and h is constant, and A is constant, E
gfor band gap.
Fig. 6 is the absorbancy curve of photocatalytic oxidation degradation tropeolin-D under simulated solar irradiation in application examples 1 of the present invention; Wherein: a
0the absorbancy curve (getting rid of the impact of photocatalyst absorption) adding after photocatalyst dark reaction half an hour, a
1, a
2, a
3, a
4it is the absorbancy curve adding after photocatalyst illumination 1h, 2h, 3h, 4h.
Fig. 7 is the absorbancy curve of photocatalytic oxidation degradation methylene blue under simulated solar irradiation in application examples 2 of the present invention; Wherein: b
0the absorbancy curve adding after photocatalyst dark reaction half an hour, b
1, b
2, b
3, b
4it is the absorbancy curve adding after photocatalyst illumination 1h, 2h, 3h, 4h.
Embodiment
Below by specific embodiment, also the present invention will be further described by reference to the accompanying drawings, but be not limited to this.
Raw materials usedly in embodiment be conventional raw material, equipment used is conventional equipment, commercial product.Wherein, electrostatic spinning apparatus used is electrostatic spinning machine; Polyvinylpyrrolidone is PVP K90, and weight-average molecular weight is 1,300,000.
Embodiment 1
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) 1g citric acid is joined in the mixing solutions being made up of 4ml dehydrated alcohol and 6ml water, sealing (avoiding water, the volatilization of ethanol equal solvent to affect result), is stirred to and dissolves completely; Add 0.15mmol ammonium molybdate and 2mmol five water Bismuth trinitrates, stir 60min; Adding 1.2ml concentration is the hydrochloric acid of 37wt%, is stirred to solution clarification, obtains bismuth molybdate solution;
(2) bismuth molybdate solution 3ml step (1) being made joins in the mixing solutions being made up of 12ml dehydrated alcohol and 3ml deionized water, stir, add 1.2g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add again the hydrochloric acid of 0.5ml37wt%, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) being made is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, the ejection speed of bismuth molybdate colloidal sol is 0.002mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning step (3) being made is placed in 60 DEG C of dry 30h of loft drier, then is placed in retort furnace and is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, and insulation calcining 60min, to obtain final product.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.5-1 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 200-500nm, and nanotube diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
As shown in Figure 5, the illustration in Fig. 5 upper right corner is that photoabsorption coefficient (α hv) is to energy (hv) variation relation figure to the diffuse reflection spectrum of γ-bismuth molybdate nanotube that the present embodiment makes; As shown in Figure 5, the extinction district of the γ-bismuth molybdate nanotube making is ultraviolet region, and energy bandgaps is 2.924eV.
Embodiment 2
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) 2g citric acid is joined in the mixing solutions being made up of 6ml dehydrated alcohol and 11ml water, sealing (avoiding water, the volatilization of ethanol equal solvent to affect result), is stirred to and dissolves completely; Add 0.29mmol ammonium molybdate and 4mmol five water Bismuth trinitrates, stir 60min; Add and get the acetic acid that 3ml concentration is 99wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) bismuth molybdate solution 2.5ml step (1) being made joins in the mixing solutions being made up of 10ml dehydrated alcohol and 2.5ml water, stir, add 1.0g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add again the acetic acid of 0.4ml99wt%, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) being made is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, the ejection speed of bismuth molybdate colloidal sol is 0.002mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning step (3) being made is placed in 60 DEG C of dry 30h of loft drier, then is placed in retort furnace and is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, and insulation calcining 60min, to obtain final product.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.5-1.5 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 200-600nm, and bismuth molybdate nanotube is made up of nano particle, has space between nano particle, has increased specific surface area.
Embodiment 3
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) 2.5g citric acid is joined in the mixing solutions being made up of 10ml dehydrated alcohol and 14ml water, sealing (avoiding the volatilization such as water, ethanol to affect result), is stirred to and dissolves completely; Add 0.36mmol ammonium molybdate and 4mmol five water Bismuth trinitrates, stir 60min; Add and get the nitric acid that 1ml concentration is 66wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) bismuth molybdate solution 2ml step (1) being made joins in the mixing solutions being made up of 8ml dehydrated alcohol and 2ml water, stir, add 0.8g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add again the nitric acid of 0.2ml66wt%, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) being made is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, the ejection speed of bismuth molybdate colloidal sol is 0.001mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning step (3) being made is placed in 60 DEG C of dry 30h of loft drier, then is placed in retort furnace and is warming up to 450 DEG C with the temperature rise rate of 1 DEG C/min, and insulation calcining 60min, to obtain final product.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.6-1.2 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 300-700nm, and nanotube diameter is even, and nano particle is in the same size.
γ-bismuth molybdate nanotube scanning X-ray diffraction spectrogram that the present embodiment is made, as shown in Figure 1.As shown in Figure 1, the γ-bismuth molybdate nanotube making is koechlinite structure.
Embodiment 4
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) 1.5g citric acid is joined in the mixing solutions being made up of 6ml dehydrated alcohol and 8.5ml water, sealing (avoiding water, the volatilization of ethanol equal solvent to affect result), is stirred to and dissolves completely; Add 1mmol ammonium molybdate and 2mmol five water Bismuth trinitrates, stir 60min; Add and get the hydrochloric acid that 1.8ml concentration is 37wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) bismuth molybdate solution 3ml step (1) being made joins in the mixing solutions being made up of 12ml dehydrated alcohol and 3ml water, stir, add 1.2g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add again the hydrochloric acid of 0.5ml37wt%, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) being made is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, the ejection speed of bismuth molybdate colloidal sol is 0.001mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning step (3) being made is placed in 60 DEG C of dry 30h of loft drier, then is placed in retort furnace and is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, and insulation calcining 60min, to obtain final product.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.5-1.2 μ m after being dried.
γ-bismuth molybdate nanotube prepared by the present embodiment carries out electron-microscope scanning, and as shown in Figure 2, as shown in Figure 2, the γ-bismuth molybdate nanotube diameter obtaining after calcining is 200-600nm, and nanotube diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
Embodiment 5
A preparation method for γ-bismuth molybdate nanotube, step is with embodiment 1, and different is;
In step (3), the voltage of electrostatic spinning is, 15kV voltage, and humidity is 15-25%, spinning receiving range is 18cm;
In step (4), drying temperature is 70 DEG C, dry 25h, and temperature rise rate is 0.5 DEG C/min, and calcining temperature is 200 DEG C, and calcination time is 180min.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.6-1.4 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 500-800nm; , nanotube diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
Embodiment 6
A preparation method for γ-bismuth molybdate nanotube, step is with embodiment 1, and different is;
In step (3), the voltage of electrostatic spinning is, 25kV voltage, and humidity is 30-40%, spinning receiving range is 22cm;
In step (4), drying temperature is 80 DEG C, dry 15h, and temperature rise rate is 2 DEG C/min, and calcining temperature is 300 DEG C, and calcination time is 120min.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.4-0.8 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 200-500nm, and nanotube diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
Embodiment 7
A preparation method for γ-bismuth molybdate nanotube, step is with embodiment 1, and different is;
In step (3), the voltage of electrostatic spinning is, 30kV voltage, and humidity is 20-30%, spinning receiving range is 25cm;
In step (4), drying temperature is 65 DEG C, dry 25h, and temperature rise rate is 4 DEG C/min, and calcining temperature is 600 DEG C, and calcination time is 80min.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.4-0.8 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 200-500nm, and nanotube diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
Embodiment 8
A preparation method for γ-bismuth molybdate nanotube, step is with embodiment 1, and different is;
In step (3), the voltage of electrostatic spinning is, 25kV voltage, and humidity is 20-30%;
In step (4), drying temperature is 70 DEG C, dry 20h, and temperature rise rate is 5 DEG C/min, and calcining temperature is 800 DEG C, and calcination time is 65min.
In the present embodiment step (4), bismuth molybdate spinning obtains gelled fibre, gelled fibre diameter 0.4-0.8 μ m after being dried; γ-bismuth molybdate nanotube the diameter obtaining after calcining is 300-600nm, and nanotube diameter is even, and surface does not have hole and crackle, intersects and forms continuously network.
The photocatalytic degradation of application examples 1, tropeolin-D
γ-bismuth molybdate nanotube prepared by embodiment 1 is applied to the photocatalytic oxidation degradation of tropeolin-D, the xenon lamp that analog light source used is 500W, and the concentration of methyl orange solution is 20mg/L, step is as follows:
First γ-bismuth molybdate nanotube of being prepared by 0.12g embodiment 1 joins in the methyl orange solution of 40ml, is then put in magnetic agitation 30min in camera bellows; Open analog light source, get 5ml solution every 60min, supernatant liquid is got in centrifugation, tests its absorbancy at climax place (464nm) with UV-2550 spectrophotometer, and presses formula (I) and calculate photocatalytic oxidation degradation efficiency.
Formula (I): η=[(A
0-A
t)/A
0] × 100%,
In formula (I), A
0for the absorbancy that solution records first, A
tthe absorbancy recording for the t time, test result as shown in Figure 6, in Fig. 6, a
0be the absorbancy curve not adding after γ-bismuth molybdate nano pipe light catalyst dark reaction half an hour, a1, a2, a3, a4 are respectively the absorbancy curve that adds the reaction of γ-bismuth molybdate nano pipe photochemical catalyst 1h, 2h, 3h, 4h.
As shown in Figure 6, γ-bismuth molybdate nanotube that prepared by embodiment 1 can photo-catalytic degradation of methyl-orange.
The photocatalytic degradation of application examples 2, methylene blue
γ-bismuth molybdate nanotube prepared by embodiment 4 is applied to the photocatalytic oxidation degradation of methylene blue, the xenon lamp that analog light source used is 500W, and the concentration of methylene blue solution is 20mg/L, step is as follows:
First γ-bismuth molybdate nanotube of being prepared by 0.12g embodiment 4 joins in the methylene blue solution of 40ml, is then put in magnetic agitation 30min in camera bellows; Open analog light source, get 5ml solution every 60min, supernatant liquid is got in centrifugation, tests its absorbancy at climax place (664nm) with UV-2550 spectrophotometer, and presses formula (I) and calculate photocatalytic oxidation degradation efficiency.
Formula (I): η=[(A
0-A
t)/A
0] × 100%,
In formula (I), A
0for the absorbancy that solution records first, A
tthe absorbancy recording for the t time, test result as shown in Figure 7, in Fig. 7, b
0be the absorbancy curve adding after γ-bismuth molybdate nano pipe light catalyst dark reaction half an hour, b1, b2, b3, b4 are respectively the absorbancy curve that adds the reaction of γ-bismuth molybdate nano pipe photochemical catalyst 1h, 2h, 3h, 4h.
As shown in Figure 7, γ-bismuth molybdate nanotube that prepared by embodiment 4 can photocatalytic degradation methylene blue.
Claims (10)
1. a preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) citric acid is joined in the mixing solutions of dehydrated alcohol and water, sealing, is stirred to and dissolves completely; Add ammonium molybdate and five water Bismuth trinitrates, stir 30-300min; Adding concentration is the acid solution of 30-50wt%, is stirred to solution clarification, obtains bismuth molybdate solution;
Described dehydrated alcohol and the volume ratio of water are (5-30): (5-30), it is (0.1-5) that described citric acid adds quality and the ratio of the volume of dehydrated alcohol: (5-30) g/ml, the mol ratio of described ammonium molybdate and five water Bismuth trinitrates is (0.01-8): (0.1-8), the molar weight of described ammonium molybdate is (0.01-8) with the ratio of the volume of dehydrated alcohol: (5-30) mol/L; Described acid solution and the volume ratio of dehydrated alcohol are (0.5-5): (5-30), described acid solution is hydrochloric acid, acetic acid or nitric acid;
(2) bismuth molybdate solution step (1) being made joins in the mixing solutions of dehydrated alcohol and water, stir, add polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add again the acid solution described in step (1), obtain bismuth molybdate colloidal sol;
The volume ratio of described bismuth molybdate solution, dehydrated alcohol and water is (0.5-5): (2-18): (1-10), it is (0.6-4) that described polyvinylpyrrolidone adds quality and the ratio of the volume of bismuth molybdate solution: (0.5-5) g/ml; The volume ratio of described acid solution and bismuth molybdate solution is (0.1-3.5): (0.5-5);
(3) bismuth molybdate colloidal sol step (2) being made is in 15-30kV voltage, and humidity is 15-50%, carries out electrostatic spinning under room temperature condition, and spinning receiving range is 15-25cm, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning step (3) being made is in 60-80 DEG C of dry 12-36h, then is warming up to 200-800 DEG C with the temperature rise rate of 0.5-5 DEG C/min, and insulation calcining 60-180min, to obtain final product.
2. the preparation method of γ-bismuth molybdate nanotube according to claim 1, it is characterized in that, the volume ratio of the dehydrated alcohol described in step (1) and water is (8-12): (8-12), it is (2-2.5) that described citric acid adds quality and the ratio of the volume of dehydrated alcohol: (8-12) g/ml.
3. the preparation method of γ-bismuth molybdate nanotube according to claim 1, it is characterized in that, the mol ratio of the ammonium molybdate described in step (1) and five water Bismuth trinitrates is (0.3-0.5): (4.5-5.5), the molar weight of described ammonium molybdate is (0.3-0.4) with the ratio of the volume of dehydrated alcohol: (8-12) mol/L.
4. the preparation method of γ-bismuth molybdate nanotube according to claim 1, is characterized in that, the volume ratio of the acid solution described in step (1) and dehydrated alcohol is (2-3): (8-12).
5. the preparation method of γ-bismuth molybdate nanotube according to claim 1, it is characterized in that, the volume ratio of bismuth molybdate solution, dehydrated alcohol and the water described in step (2) is (2-3): (8-12): (2-5).
6. the preparation method of γ-bismuth molybdate nanotube according to claim 1, it is characterized in that, it is (0.6-1.2) that the polyvinylpyrrolidone described in step (2) adds quality and the ratio of the volume of bismuth molybdate solution: (2-3) g/ml.
7. the preparation method of γ-bismuth molybdate nanotube according to claim 1, is characterized in that, the volume ratio of the acid solution described in step (2) and bismuth molybdate solution is (0.1-1.0): (2-3).
8. the preparation method of γ-bismuth molybdate nanotube according to claim 1, is characterized in that, in step (3), electrostatic spinning voltage is 18-25kV voltage, and humidity is 20-35%.
9. the preparation method of γ-bismuth molybdate nanotube according to claim 1, it is characterized in that, in step (3), electrostatic spinning is, with the plastic injector with stainless steel syringe needle, bismuth molybdate colloidal sol is sprayed onto to electrostatic spinning in dash receiver, and ejection speed is 0.001-0.002mm/s; Distance between syringe needle and the dash receiver of syringe is 18-22cm, and syringe needle internal diameter is 0.3-0.9mm.
10. the preparation method of γ-bismuth molybdate nanotube according to claim 1, is characterized in that, in step (4), drying temperature is 50-80 DEG C; Temperature rise rate is 1-3 DEG C/min, and calcining temperature is 300-700 DEG C, insulation 90-150min.
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