CN104192907B - The preparation method of a kind of γ-bismuth molybdate nanotube - Google Patents
The preparation method of a kind of γ-bismuth molybdate nanotube Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of γ-bismuth molybdate nanotube.First citric acid is joined in dehydrated alcohol and water, sealing, dissolve completely; Add ammonium molybdate, five water Bismuth trinitrate and acid solutions, obtain bismuth molybdate solution; Again bismuth molybdate solution is joined in dehydrated alcohol and water, stir, add polyvinylpyrrolidone and dissolve completely, add acid solution, obtain bismuth molybdate colloidal sol; Then bismuth molybdate colloidal sol is carried out electrostatic spinning, obtain bismuth molybdate spinning; Finally that bismuth molybdate spinning is dry, be warming up to 200-800 DEG C, insulation calcining 60-180min, to obtain final product.Sheet γ-bismuth molybdate that γ-bismuth molybdate nanotube prepared by electrostatic spinning of the present invention is prepared than sol-gel method can better be degraded tropeolin-D, methylene blue etc., and preparation method's step is simple, with low cost, and the diameter of nanotube is easy to control.
Description
Technical field
The present invention relates to the preparation method of a kind of γ-bismuth molybdate nanotube, belong 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, and having energy band structure and high photo-generated carrier movability that responding to visible light excites, is a kind of excellent novel photocatalysis material.
Current γ-Bi
2moO
6main preparation methods have solid phase method (see: Chinese patent literature CN102345163A), hydrothermal method is (see Chinese Journal of Inorganic Chemistry, 2009,25 (3), 512), solvent-thermal method is (see JournalofNanoscienceandNanotechnology, 2011,, 10,4168) sol-gel method is (see Acta PhySico-Chimica Sinica 2007,23 (11); 1671) γ-Bi is etc., synthesized by these methods
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 limit its use range.
Nanotube-shaped material due to its uniqueness physical and chemical performance and in fields such as catalysis, medicine, nanoelectronic, opto-electronic devices, there is potential using value and cause showing great attention to of investigators, scientists is exploring the preparation method of hollow structure nanofiber always.Zhang etc. describe and adopt electrostatic spinning technique to prepare γ-Bi in conjunction with solvent thermal process
2moO
6micron tube (see: JournalofHazardousMaterials2012,225,166), its preparation process is roughly and first adopts electrostatic spinning technique to prepare polyacrylonitrile and 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 removing PAN masterplate obtains γ-Bi
2moO
6micron tube.Due to when the core to PAN/BMO calcining removing PAN, toxic substance can be produced; 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 design one simply, γ-Bi fast
2moO
6the preparation method of nanotube, has potential theoretical significance and useful application is worth.
The method is compared with traditional template synthesis method preparing tubular structure nanofiber, and step is more simple, and a step just can be prepared.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of a kind 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, be stirred to and dissolve completely; Add ammonium molybdate and five water Bismuth trinitrates, stir 30-300min; Add the acid solution that concentration is 30-50wt%, be stirred to solution clarification, obtain 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 with 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), and 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), and described acid solution is hydrochloric acid, acetic acid or nitric acid;
(2) the bismuth molybdate solution that step (1) is obtained is joined in the mixing solutions of dehydrated alcohol and water, stir, add polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add the acid solution described in step (1) again, 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), and it is (0.6-4) that described polyvinylpyrrolidone adds quality with 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) obtained 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) obtained 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 with 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), and 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), and it is (0.6-1.2) that described polyvinylpyrrolidone adds quality with 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, preferably, 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, with the plastic injector of band stainless steel syringe needle, bismuth molybdate colloidal sol is sprayed onto electrostatic spinning in dash receiver, ejection speed is 0.001-0.002mm/s; Distance (i.e. spinning receiving range) between the syringe needle of syringe and dash receiver is preferably 18-22cm, more preferably 20cm; The preferred 0.3-0.9mm of syringe needle internal diameter.
According to the present invention, preferably, 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, obtains bismuth molybdate gelled fibre, gelled fibre diameter 0.5-2 μm by after bismuth molybdate spinning drying, and after calcining, tube diameters is 200-800nm.
γ-bismuth molybdate that the present invention obtains is sodium nanotube structures, uniform diameter, and surface does not have hole and crackle, intersects and forms network continuously.
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 be degraded 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 be formed; Preferably spinning condition makes nanofiber diameter even; Preferably calcination condition avoids the fracture of nanotube and the doping of a large amount of particulate material.
4, γ-bismuth molybdate nanotube of preparing of the present invention is 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.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram (XRD) of γ-bismuth molybdate nanotube that the embodiment of the present invention 3 obtains.
Fig. 2 is scanning electron microscope (SEM) figure of γ-bismuth molybdate nanotube that the embodiment of the present invention 4 obtains.
Fig. 3 is the illustration in scanning electron microscope (SEM) figure, Fig. 3 upper left corner of γ-bismuth molybdate nanotube that the embodiment of the present invention 1 obtains is transmission electron microscope (TEM) figure.
Fig. 4 is scanning electron microscope (SEM) figure of γ-bismuth molybdate nanotube that the embodiment of the present invention 2 obtains.
Fig. 5 is the diffuse reflection spectrum of the obtained γ-bismuth molybdate nanotube of the embodiment of the present invention 1, the illustration in Fig. 5 upper right corner be photoabsorption coefficient (α hv) 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 absorbance curve of photocatalytic oxidation degradation tropeolin-D under simulated solar irradiation in application examples 1 of the present invention; Wherein: a
0the absorbance curve (getting rid of the impact of photocatalyst absorption) after adding photocatalyst dark reaction half an hour, a
1, a
2, a
3, a
4it is the absorbance curve after adding photocatalyst illumination 1h, 2h, 3h, 4h.
Fig. 7 is the absorbance curve of photocatalytic oxidation degradation methylene blue under simulated solar irradiation in application examples 2 of the present invention; Wherein: b
0the absorbance curve after adding photocatalyst dark reaction half an hour, b
1, b
2, b
3, b
4it is the absorbance curve after adding 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 thereto.
Raw materials usedly in embodiment be convenient source, equipment used is conventional equipment, commercial products.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) joined by 1g citric acid in the mixing solutions be made up of 4ml dehydrated alcohol and 6ml water, sealing (avoid water, ethanol equal solvent to volatilize and affect result), is stirred to and dissolves completely; Add 0.15mmol ammonium molybdate and 2mmol five water Bismuth trinitrate, stir 60min; Add the hydrochloric acid that 1.2ml concentration is 37wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) the bismuth molybdate solution that 3ml step (1) is obtained is joined in the mixing solutions be made up of 12ml dehydrated alcohol and 3ml deionized water, stir, add 1.2g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add the hydrochloric acid of 0.5ml37wt% again, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) obtained is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, and the ejection speed of bismuth molybdate colloidal sol is 0.002mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning obtained for step (3) is placed in loft drier 60 DEG C of dry 30h, then is placed in retort furnace and is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation calcining 60min, to obtain final product.
Gelled fibre is obtained, gelled fibre diameter 0.5-1 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 200-500nm, and tube diameters is even, and surface does not have hole and crackle, intersects and forms network continuously.
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 the γ that the present embodiment obtains-bismuth molybdate nanotube; As shown in Figure 5, the extinction district of obtained γ-bismuth molybdate nanotube is ultraviolet region, and energy bandgaps is 2.924eV.
Embodiment 2
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) joined by 2g citric acid in the mixing solutions be made up of 6ml dehydrated alcohol and 11ml water, sealing (avoid water, ethanol equal solvent to volatilize and affect result), is stirred to and dissolves completely; Add 0.29mmol ammonium molybdate and 4mmol five water Bismuth trinitrate, stir 60min; Add and get the acetic acid that 3ml concentration is 99wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) the bismuth molybdate solution that 2.5ml step (1) is obtained is joined in the mixing solutions be made up of 10ml dehydrated alcohol and 2.5ml water, stir, add 1.0g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add the acetic acid of 0.4ml99wt% again, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) obtained is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, and the ejection speed of bismuth molybdate colloidal sol is 0.002mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning obtained for step (3) is placed in loft drier 60 DEG C of dry 30h, then is placed in retort furnace and is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation calcining 60min, to obtain final product.
Gelled fibre is obtained, gelled fibre diameter 0.5-1.5 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 200-600nm, and bismuth molybdate nanotube is made up of nano particle, has space between nano particle, increases specific surface area.
Embodiment 3
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) joined by 2.5g citric acid in the mixing solutions be made up of 10ml dehydrated alcohol and 14ml water, sealing (avoid water, ethanol etc. to volatilize and affect result), is stirred to and dissolves completely; Add 0.36mmol ammonium molybdate and 4mmol five water Bismuth trinitrate, stir 60min; Add and get the nitric acid that 1ml concentration is 66wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) the bismuth molybdate solution that 2ml step (1) is obtained is joined in the mixing solutions be made up of 8ml dehydrated alcohol and 2ml water, stir, add 0.8g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add the nitric acid of 0.2ml66wt% again, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) obtained is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, and the ejection speed of bismuth molybdate colloidal sol is 0.001mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning obtained for step (3) is placed in loft drier 60 DEG C of dry 30h, then is placed in retort furnace and is warming up to 450 DEG C with the temperature rise rate of 1 DEG C/min, insulation calcining 60min, to obtain final product.
Gelled fibre is obtained, gelled fibre diameter 0.6-1.2 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 300-700nm, and tube diameters is even, and nano particle is in the same size.
γ-bismuth molybdate nanotube scanning X-ray diffraction the spectrogram obtained to the present embodiment, as shown in Figure 1.As shown in Figure 1, obtained γ-bismuth molybdate nanotube is koechlinite structure.
Embodiment 4
A preparation method for γ-bismuth molybdate nanotube, step is as follows:
(1) joined by 1.5g citric acid in the mixing solutions be made up of 6ml dehydrated alcohol and 8.5ml water, sealing (avoid water, ethanol equal solvent to volatilize and affect result), is stirred to and dissolves completely; Add 1mmol ammonium molybdate and 2mmol five water Bismuth trinitrate, stir 60min; Add and get the hydrochloric acid that 1.8ml concentration is 37wt%, be stirred to solution clarification, obtain bismuth molybdate solution;
(2) the bismuth molybdate solution that 3ml step (1) is obtained is joined in the mixing solutions be made up of 12ml dehydrated alcohol and 3ml water, stir, add 1.2g polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, add the hydrochloric acid of 0.5ml37wt% again, obtain bismuth molybdate colloidal sol;
(3) bismuth molybdate colloidal sol step (2) obtained is in 20kV voltage, and humidity is 20-35%, electrostatic spinning under room temperature condition, and spinning receiving range is 20cm, and the ejection speed of bismuth molybdate colloidal sol is 0.001mm/s, obtains bismuth molybdate spinning;
(4) bismuth molybdate spinning obtained for step (3) is placed in loft drier 60 DEG C of dry 30h, then is placed in retort furnace and is warming up to 500 DEG C with the temperature rise rate of 1 DEG C/min, insulation calcining 60min, to obtain final product.
Gelled fibre is obtained, gelled fibre diameter 0.5-1.2 μm after bismuth molybdate spinning drying in the present embodiment step (4).
Carry out electron-microscope scanning to γ-bismuth molybdate nanotube prepared by the present embodiment, as shown in Figure 2, as shown in Figure 2, the γ obtained after calcining-bismuth molybdate tube diameters is 200-600nm, and tube diameters is even, and surface does not have hole and crackle, intersects and forms network continuously.
Embodiment 5
A preparation method for γ-bismuth molybdate nanotube, step with embodiment 1, unlike;
In step (3), the voltage of electrostatic spinning is, 15kV voltage, and humidity is 15-25%, and spinning receiving range is 18cm;
In step (4), drying temperature is 70 DEG C, and dry 25h, temperature rise rate is 0.5 DEG C/min, and calcining temperature is 200 DEG C, and calcination time is 180min.
Gelled fibre is obtained, gelled fibre diameter 0.6-1.4 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 500-800nm; , tube diameters is even, and surface does not have hole and crackle, intersects and forms network continuously.
Embodiment 6
A preparation method for γ-bismuth molybdate nanotube, step with embodiment 1, unlike;
In step (3), the voltage of electrostatic spinning is, 25kV voltage, and humidity is 30-40%, and spinning receiving range is 22cm;
In step (4), drying temperature is 80 DEG C, and dry 15h, temperature rise rate is 2 DEG C/min, and calcining temperature is 300 DEG C, and calcination time is 120min.
Gelled fibre is obtained, gelled fibre diameter 0.4-0.8 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 200-500nm, and tube diameters is even, and surface does not have hole and crackle, intersects and forms network continuously.
Embodiment 7
A preparation method for γ-bismuth molybdate nanotube, step with embodiment 1, unlike;
In step (3), the voltage of electrostatic spinning is, 30kV voltage, and humidity is 20-30%, and spinning receiving range is 25cm;
In step (4), drying temperature is 65 DEG C, and dry 25h, temperature rise rate is 4 DEG C/min, and calcining temperature is 600 DEG C, and calcination time is 80min.
Gelled fibre is obtained, gelled fibre diameter 0.4-0.8 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 200-500nm, and tube diameters is even, and surface does not have hole and crackle, intersects and forms network continuously.
Embodiment 8
A preparation method for γ-bismuth molybdate nanotube, step with embodiment 1, unlike;
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, and dry 20h, temperature rise rate is 5 DEG C/min, and calcining temperature is 800 DEG C, and calcination time is 65min.
Gelled fibre is obtained, gelled fibre diameter 0.4-0.8 μm after bismuth molybdate spinning drying in the present embodiment step (4); The γ obtained after calcining-bismuth molybdate tube diameters is 300-600nm, and tube diameters is even, and surface does not have hole and crackle, intersects and forms network continuously.
The photocatalytic degradation of application examples 1, tropeolin-D
γ embodiment 1 prepared-bismuth molybdate nanotube is applied to the photocatalytic oxidation degradation of tropeolin-D, and analog light source used is the xenon lamp of 500W, and the concentration of methyl orange solution is 20mg/L, and step is as follows:
First γ-bismuth molybdate nanotube prepared by 0.12g embodiment 1 is joined in the methyl orange solution of 40ml, be 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), and calculate photocatalytic oxidation degradation efficiency by formula (I) with UV-2550 spectrophotometer.
Formula (I): η=[(A
0-A
t)/A
0] × 100%,
In formula (I), A
0for the absorbancy that solution records first, A
tfor the absorbancy that the t time records, test result as shown in Figure 6, in Fig. 6, a
0be the absorbance curve after not adding γ-bismuth molybdate nano pipe light catalyst dark reaction half an hour, a1, a2, a3, a4 are respectively the absorbance curve adding the γ-reaction of 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 embodiment 4 prepared-bismuth molybdate nanotube is applied to the photocatalytic oxidation degradation of methylene blue, and analog light source used is the xenon lamp of 500W, and the concentration of methylene blue solution is 20mg/L, and step is as follows:
First γ-bismuth molybdate nanotube prepared by 0.12g embodiment 4 is joined in the methylene blue solution of 40ml, be 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), and calculate photocatalytic oxidation degradation efficiency by formula (I) with UV-2550 spectrophotometer.
Formula (I): η=[(A
0-A
t)/A
0] × 100%,
In formula (I), A
0for the absorbancy that solution records first, A
tfor the absorbancy that the t time records, test result as shown in Figure 7, in Fig. 7, b
0be the absorbance curve after adding γ-bismuth molybdate nano pipe light catalyst dark reaction half an hour, b1, b2, b3, b4 are respectively the absorbance curve adding the γ-reaction of 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. one kind
γ-the preparation method of bismuth molybdate nanotube, step is as follows:
(1) citric acid is joined in the mixing solutions of dehydrated alcohol and water, sealing, be stirred to and dissolve completely; Add ammonium molybdate and five water Bismuth trinitrates, stir 30-300min; Add the acid solution that concentration is 30-50wt%, be stirred to solution clarification, obtain 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 with 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), and 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), and described acid solution is hydrochloric acid, acetic acid or nitric acid;
(2) the bismuth molybdate solution that step (1) is obtained is joined in the mixing solutions of dehydrated alcohol and water, stir, add polyvinylpyrrolidone (PVP), be stirred to and dissolve completely, then add 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), and it is (0.6-4) that described polyvinylpyrrolidone adds quality with 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) obtained 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) obtained 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
γ-bismuth molybdate nanotube.
2. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, is characterized in that, the volume ratio of the dehydrated alcohol described in step (1) and water is (8-12): (8-12), and it is (2-2.5) that described citric acid adds quality with the ratio of the volume of dehydrated alcohol: (8-12) g/mL.
3. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, 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), and 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. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, is characterized in that, the volume ratio of the acid solution described in step (1) and dehydrated alcohol is (2-3): (8-12).
5. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, 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. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, is characterized in that, it is (0.6-1.2) that the polyvinylpyrrolidone described in step (2) adds quality with the ratio of the volume of bismuth molybdate solution: (2-3) g/mL.
7. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, 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. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, is characterized in that, in step (3), electrostatic spinning voltage is 18-25kV voltage, and humidity is 20-35%.
9. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, is characterized in that, in step (3), electrostatic spinning is, with the plastic injector of band stainless steel syringe needle, bismuth molybdate colloidal sol is sprayed onto electrostatic spinning in dash receiver, and ejection speed is 0.001-0.002mm/s; Distance between the syringe needle of syringe and dash receiver is 18-22cm, and syringe needle internal diameter is 0.3-0.9mm.
10. according to claim 1
γ-the preparation method of bismuth molybdate nanotube, is characterized in that, in step (4), drying temperature is 60-80 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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