CN103276474A - Method for preparing (Ga1-xZnx)(N1-xOx) nano fiber by electrostatic spinning method - Google Patents

Method for preparing (Ga1-xZnx)(N1-xOx) nano fiber by electrostatic spinning method Download PDF

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CN103276474A
CN103276474A CN2013101954027A CN201310195402A CN103276474A CN 103276474 A CN103276474 A CN 103276474A CN 2013101954027 A CN2013101954027 A CN 2013101954027A CN 201310195402 A CN201310195402 A CN 201310195402A CN 103276474 A CN103276474 A CN 103276474A
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nanofiber
gallium
zinc
electrostatic spinning
salt
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CN103276474B (en
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张青红
李雪冬
王宏志
李耀刚
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Donghua University
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Abstract

The invention relates to a method for preparing a (Ga1-xZnx)(N1-xOx) nano fiber by an electrostatic spinning method. The method comprises the following steps of: (1) dispersing zinc salt, gallium salt and PVP (Polyvinyl Pyrrolidone) into a mixed solution of ethanol and water; violently agitating to completely dissolve the zinc salt, the gallium salt and the PVP to form uniform and transparent gel; (2) carrying out electrostatic spinning on the gel to obtain a zinc-gallium organic salt/PVP compound nano fiber; (3) calcining the zinc-gallium organic salt/PVP compound nano fiber and naturally cooling to a room temperature to obtain a zinc-gallium compound oxide nano fiber; and (4) placing the zinc-gallium compound oxide nano fiber into a flowing ammonia atmosphere to be nitrided. According to the method disclosed by the invention, the needed reaction temperature is low and the reaction time is greatly shortened; the diameter of the prepared (Ga1-xZnx)(N1-xOx) nano fiber is uniformly distributed, the size of a crystal grain is small and the specific surface area is high; water can be decomposed into hydrogen and oxygen under visible light irradiation.

Description

Method of electrostatic spinning preparation (Ga 1-xZn x) (N 1-xO x) method of nanofiber
Technical field
The invention belongs to (Ga 1-xZn x) (N 1-xO x) preparation field of nanofiber, particularly a kind of method of electrostatic spinning preparation (Ga 1-xZn x) (N 1-xO x) method of nanofiber.
Background technology
(Ga 1-xZn x) (N 1-xO x) be a kind of stable solid solution that is constituted by ZnO and GaN, its energy gap is narrower, is about 2.4～2.8eV, and it is adjustable to have visible absorption activity and absorption spectrum ranges, is emerging in recent years a kind of visible light catalytic semi-conducting material.(Ga 1-xZn x) (N 1-xO x) conduction band at the bottom of formed by Ga4s4p, top of valence band is made of N2p and Zn3d hybridized orbit, can by regulate Zn, the Ga component ratio be regulated and control its performance.And its stable chemical performance has significant visible light catalytic hydrogen production by water decomposition activity behind the load cocatalyst, has important prospect in realizing solar hydrogen making.
(Ga at present 1-xZn x) (N 1-xO x) the preparation method be mainly high temperature solid-state method, be raw material with two kinds of oxide micropowders namely, obtain (the Ga of micro powder grade through high-temperature ammonolysis 1-xZn x) (N 1-xO x).The Domen of Tokyo University etc. are at Nature, have reported with ZnO and Ga on 2006,440,295 2O 3Powder is raw material, has prepared (Ga through high temperature solid state reaction 1-xZn x) (N 1-xO x) particle.The raw material crystallite dimension that this method is selected for use is big, and need being not less than nitridation reaction temperature, time of 850 ℃, to grow to the nitrogenize of 15 hours ability complete, resulting (Ga 1-xZn x) (N 1-xO x) crystal grain is big, particle size distribution is wide, specific area is very low (is up to 7～8m 2/ g), in the visible light catalytic reaction, do not embody the gain effect of small-size effect.
Electrostatic spinning nano fiber has unique network structure, high draw ratio, and high advantages such as specific area can provide more reaction active site for nitridation reaction.Thereby the nanofiber that is equipped with electro-spinning is presoma, can effectively reduce reaction temperature in the nitridation process, significantly shorten the reaction time, obtains crystallite dimension is little, specific area is high nitrogen oxide or nitride nano fiber.In addition, in calcination process, along with removing of high polymer, also be of value to the raising of material specific area at the nano-pore of fiber surface and inner formation.The Pan of Tsing-Hua University etc. have reported (the NO with Ga at Adv.Mater. on 2009,21, the 227-231 3) 3With PVP be raw material, be solvent with water and ethanol, through static spin, calcining and nitridation process make the gallium nitride nanofiber, the GaN nanofiber of gained has photoluminescence performance.But up to now, about method of electrostatic spinning preparation (Ga 1-xZn x) (N 1-xO x) document of nanofiber do not appear in the newspapers as yet.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of electrostatic spinning preparation (Ga 1-xZn x) (N 1-xO x) method of nanofiber, this method can obviously reduce preparation (Ga 1-xZn x) (N 1-xO x) required reaction temperature is low, significantly shorten the reaction time, and (the Ga that makes 1-xZn x) (N 1-xO x) the nanofiber diameter homogeneous, crystallite dimension is little and grain size distribution narrow range, specific area height.
A kind of method of electrostatic spinning preparation (Ga of the present invention 1-xZn x) (N 1-xO x) method of nanofiber, comprising:
(1) at room temperature, zinc salt, gallium salt, polyvinylpyrrolidone PVP are distributed in the mixed solution of second alcohol and water, vigorous stirring 12～24h dissolves it fully and forms the homogeneous transparent gel;
(2) above-mentioned gel is carried out electrostatic spinning, obtain zinc gallium inorganic salts/PVP composite nano fiber;
(3) preparation of composite oxides nanofiber: above-mentioned zinc gallium inorganic salts/PVP composite nano fiber is calcined, naturally cooled to room temperature, namely get zinc gallium composite oxides nanofiber;
(4) nitrogenize of composite oxides nanofiber:
Above-mentioned zinc gallium composite oxides nanofiber is placed mobile ammonia atmosphere nitrogenize, and question response finishes to naturally cool to room temperature, obtains (Ga 1-xZn x) (N 1-xO x) nanofiber.This nanofiber specific area height, diameter are even, the little and Size Distribution narrow range of crystallite dimension, and nitrogenize product (Ga 1-xZn x) (N 1-xO x) in Zn, Ga than the rate of charge close to Zn, Ga in the raw material (zinc salt, gallium salt).
(5) (Ga 1-xZn x) (N 1-xO x) the visible light catalytic hydrogen manufacturing performance of nanofiber
With (Ga 1-xZn x) (N 1-xO x) behind the nanofiber area load co-catalyst, be dispersed in the aqueous sulfuric acid of pH=4.5, place in the reaction unit.Behind the radiation of visible light certain hour, the gaseous product in the catalyst reaction device is sent in the gas-chromatography, quantitatively the hydrogen output of detection reaction generation.
The volume ratio of ethanol and water is 1:1～9:1 in the mixed solution described in the step (1).
Zinc salt described in the step (1), the concentration of gallium salt in mixed solution are respectively 0.05～0.3mol/L.
Zinc salt described in the step (1) and gallium salt water soluble and ethanol, the mol ratio of zinc salt and gallium salt is 1:5～5:1.
The mass ratio of zinc salt described in the step (1) and gallium salt sum and PVP is 1:2～2:1; The molecular weight of PVP is 30000-1300000.
The technological parameter of the electrostatic spinning described in the step (2) is: described gel is poured in the syringe, then described syringe is fixed on the miniflow pump, advancing speed is 5～30 μ L/min, nozzle is 10～20cm with the distance that receives aluminium foil or wire netting, add 10～20kV electrostatic field and carry out spinning between nozzle and reception aluminium foil or wire netting, ambient humidity control is 15%～25% during spinning.
Heating rate is 2～8 ℃/min in the calcining described in the step (3), and calcining heat is 400～600 ℃, and temperature retention time is 3～6h.
Ammonia flow is 200～400mL/min in the ammonia atmosphere nitrogenize described in the step (4), and nitridation conditions is that heating rate is 2～8 ℃/min, and nitriding temperature is 400～845 ℃, and temperature retention time is 3～10h.
Beneficial effect:
(1) can obviously reduce preparation (Ga 1-xZn x) (N 1-xO x) required nitridation reaction temperature (can be low to moderate 700 ℃), significantly shorten the reaction time, cut down the consumption of energy.
(2) can prepare (the Ga of a series of Different Zinc gallium ratios 1-xZn x) (N 1-xO x) nanofiber, and nitrogenize product (Ga 1-xZn x) (N 1-xO x) in Zn, Ga than the rate of charge close to Zn, Ga in the raw material (zinc salt, gallium salt).
(3) Zhi Bei (Ga 1-xZn x) (N 1-xO x) the nanofiber diameter homogeneous, in 80～100nm scope, the little and Size Distribution narrow range of crystallite dimension, specific area can be up to 85.5m 2/ g; (Ga with the preparation of high-temperature ammonolysis method 1-xZn x) (N 1-xO x) micro mist is compared has more excellent visible light catalytic decomposition water hydrogen manufacturing performance.
Description of drawings
Fig. 1 is (Ga 1-xZn x) (N 1-xO x) transmission electron microscope photo of nanofiber;
Fig. 2 is (Ga 1-xZn x) (N 1-xO x) the nanofiber X-ray diffractogram;
Fig. 3 is (Ga 1-xZn x) (N 1-xO x) the ultraviolet-visible diffuse reflection absorption spectrum of nanofiber;
Fig. 4 is (Ga 1-xZn x) (N 1-xO x) isothermal nitrogen adsorption-desorption curve of nanofiber;
Fig. 5 is (Ga 1-xZn x) (N 1-xO x) the visible light catalytic hydrogen production by water decomposition rate curve of nanofiber.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) takes by weighing 0.5950g Zn (NO 3) 26H 2O, 0.5115g Ga (NO 3) 3XH 2O and 1.1064g PVP(number-average molecular weight Mn=1300000), (ethanol: in the water=1:1), 400 commentaries on classics/min magnetic agitation 18h under the room temperature are until Zn (NO to join 10mL ethanol, water mixed solution 3) 26H 2O, Ga (NO 3) 3XH 2O and PVP dissolve fully, form bubble-free homogeneous solution, wherein Zn 2+: Ga 3+=1:1(mol ratio), inorganic salts: the PVP=1:1(mass ratio), absolute ethyl alcohol: deionized water=5:5(volume ratio).
(2) with in the solution injected plastic syringe, being fixed on the micro-fluid pump, is dash receiver with the wire netting, and at the fltting speed of 10 μ L/min, the electrostatic field of 15kV obtains zinc gallium inorganic salts/PVP composite nano fiber under the acceptance distance of 18cm.
(3) culture dish is put in above-mentioned zinc gallium inorganic salts/PVP composite nano fiber tiling, placed Muffle furnace, temperature increasing schedule is: be warming up to 200 ℃ from room temperature, heating rate is 8 ℃/min; Be warming up to 250 ℃ from 200 ℃, heating rate is 2 ℃/min; Be warming up to 500 ℃ from 250 ℃, heating rate is 5 ℃/min; At 500 ℃ of insulation 4h, naturally cool to room temperature subsequently, obtain zinc gallium mixed oxide nanoparticle fiber.
(4) zinc gallium mixed oxide nanoparticle fiber is put into the tubular type atmosphere furnace, feed the ammonia that flows, ammonia flow remains on 400mL/min, is raised to 700 ℃ from room temperature, and heating rate is 5 ℃/min, and insulation 4h naturally cools to room temperature subsequently, obtains (Ga 1-xZn x) (N 1-xO x) nanofiber.
Fig. 1 is the (Ga of present embodiment preparation 1-xZn x) (N 1-xO x) transmission electron microscope photo of nanofiber, show (the Ga of preparation 1-xZn x) (N 1-xO x) nanofiber is even thickness, diameter is about 80～100nm, the crystallite dimension size in 20nm, grain size distribution narrow range, and distributing of uniform size mesoporous equably at fiber surface and inside.
Fig. 2 is the (Ga of present embodiment preparation 1-xZn x) (N 1-xO x) X-ray diffractogram of nanofiber, the nanofiber of present embodiment preparation is the (Ga of hexagonal wurtzite structure as can be seen from the position of diffraction maximum 1-xZn x) (N 1-xO x), do not have other impurity and exist mutually.
Fig. 3 is the (Ga of present embodiment preparation 1-xZn x) (N 1-xO x) the ultraviolet-visible diffuse reflection absorption spectrum of nanofiber, the as can be seen from the figure (Ga of the implementation case preparation 1-xZn x) (N 1-xO x) nanofiber has strong absorption in the visible region.Specific area and pore-size distribution the test shows: (Ga that the implementation case is prepared 1-xZn x) (N 1-xO x) the nanofiber specific area is 73.0m 2/ g, average pore size is 13.9nm, belongs to mesoporous category.
Embodiment 2
(1) takes by weighing 0.6319g Zn (CH 3COO) 22H 2O, 0.3681g Ga (NO 3) 3XH 2O and 1g PVP(number-average molecular weight Mn=1300000), (ethanol: in the water=4:1), 400 commentaries on classics/min magnetic agitation 18h under the room temperature are until Zn (CH to join 10mL ethanol, water mixed solution 3COO) 22H 2O, Ga (NO 3) 3XH 2O and PVP dissolve fully, form bubble-free homogeneous solution, wherein Zn 2+: Ga 3+=2:1(mol ratio), inorganic salts: the PVP=1:1(mass ratio), absolute ethyl alcohol: deionized water=8:2(volume ratio).
(2) with in the solution injected plastic syringe, being fixed on the micro-fluid pump, is dash receiver with the aluminium foil, and at the fltting speed of 6 μ L/min, the electrostatic field of 18kV obtains zinc gallium inorganic salts/PVP composite nano fiber under the acceptance distance of 20cm.
(3) culture dish is put in above-mentioned zinc gallium inorganic salts/PVP composite nano fiber tiling, placed Muffle furnace, temperature increasing schedule is: be warming up to 200 ℃ from room temperature, heating rate is 8 ℃/min; Be warming up to 250 ℃ from 200 ℃, heating rate is 2 ℃/min; Be warming up to 500 ℃ from 250 ℃, heating rate is 5 ℃/min; At 500 ℃ of insulation 5h, naturally cool to room temperature subsequently, obtain zinc gallium mixed oxide nanoparticle fiber.
(4) zinc gallium mixed oxide nanoparticle fiber is put into the tubular type atmosphere furnace, feed the ammonia that flows, ammonia flow remains on 400mL/min, is raised to 700 ℃ from room temperature, and heating rate is 5 ℃/min, and insulation 4h naturally cools to room temperature subsequently, obtains (Ga 1-xZn x) (N 1-xO x) nanofiber.
Fig. 4 is the (Ga of present embodiment preparation 1-xZn x) (N 1-xO x) isothermal nitrogen adsorption-desorption curve of nanofiber, be the isothermal curve of typical mesoporous material.Specific area and pore-size distribution the test shows: (Ga that the implementation case is prepared 1-xZn x) (N 1-xO x) the nanofiber specific area is 85.5m 2/ g, average pore size is 8.0nm, belongs to mesoporous category.
Embodiment 3
(1) takes by weighing 0.5950g Zn (NO 3) 26H 2O, 0.5115g Ga (NO 3) 3XH 2O and 1.1064g PVP(number-average molecular weight Mn=1300000), (ethanol: in the water=3:2), 400 commentaries on classics/min magnetic agitation 24h under the room temperature are until Zn (NO to join 10mL ethanol, water mixed solution 3) 26H 2O, Ga (NO 3) 3XH 2O and PVP dissolve fully, form bubble-free homogeneous solution, wherein Zn 2+: Ga 3+=1:1(mol ratio), inorganic salts: the PVP=1:1(mass ratio), absolute ethyl alcohol: deionized water=6:4(volume ratio).
(2) with in the solution injected plastic syringe, being fixed on the micro-fluid pump, is dash receiver with the wire netting, and at the fltting speed of 20 μ L/min, the electrostatic field of 18kV obtains zinc gallium inorganic salts/PVP composite nano fiber under the acceptance distance of 18cm.
(3) culture dish is put in above-mentioned zinc gallium inorganic salts/PVP composite nano fiber tiling, placed Muffle furnace, be warming up to 500 ℃ from room temperature, heating rate is 4 ℃/min, insulation 4h guarantees that PVP removes fully, naturally cools to room temperature subsequently, obtains zinc gallium mixed oxide nanoparticle fiber.
(4) zinc gallium mixed oxide nanoparticle fiber is put into the tubular type atmosphere furnace, feed the ammonia that flows, ammonia flow remains on 400mL/min, is raised to 700 ℃ from room temperature, and heating rate is 5 ℃/min, and insulation 5h naturally cools to room temperature subsequently, obtains (Ga 1-xZn x) (N 1-xO x) nanofiber.
Specific area and pore-size distribution the test shows: (Ga that the implementation case is prepared 1-xZn x) (N 1-xO x) the nanofiber specific area is 51.9m 2/ g, average pore size is 16.6nm, belongs to mesoporous category.
Embodiment 4
The sample of embodiment 2 preparations is used as catalyst visible light catalytic hydrogen production by water decomposition gas, is light source with the 300W xenon lamp, adopts the JZ-420 optical filter with the light filtering below the 420nm.Take by weighing the 0.1g sample and add 100mL H 2O(H 2SO 4Regulate pH=4.5) in, ultrasonic dispersion 30min is dispersed in the water sample.Sample suspension is placed the light-catalyzed reaction bottle, insert photocatalytic hydrogen production by water decomposition reaction on-line acquisition system (model is Labsolar-III AG, Beijing pool Fei Lai Science and Technology Ltd.), open light source then and carry out light-catalyzed reaction.Every 1h the gas in the reaction system is quantitatively sent into by six-way valve in the gas-chromatography (model is GC7900, Shanghai Techcomp Instrument Ltd.), adopted the hydrogen content in the quantitative detection reaction gaseous product of TCD detector.The parameter of gas-chromatography is set to: 80 ℃ of post oven temperature, degree, and 120 ℃ of injector temperatures, 120 ℃ of detector temperatures detect electric current 80mA, and carrier gas is high pure nitrogen N 2(purity 99.999%).
Fig. 5 is (Ga in the present embodiment 1-xZn x) (N 1-xO x) nanofiber is as the visible light catalytic hydrogen production by water decomposition rate curve of catalyst.As can be seen from Figure, (Ga 1-xZn x) (N 1-xO x) nanofiber is hydrogen with water decomposition under radiation of visible light, under catalytic reaction condition, has (the Ga than high temperature solid-state-vapor phase method preparation 1-xZn x) (N 1-xO x) (850 ℃ of nitriding temperatures, reaction time 15h, raw material are commercially available ZnO and Ga to the micro mist sample 2O 3Micro mist) higher visible light catalytic hydrogen production efficiency.

Claims (8)

1. a method of electrostatic spinning prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, comprising:
(1) at room temperature, zinc salt, gallium salt, polyvinylpyrrolidone PVP are distributed in the mixed solution of second alcohol and water, vigorous stirring 12～24h dissolves it fully and forms the homogeneous transparent gel;
(2) above-mentioned gel is carried out electrostatic spinning, obtain zinc gallium inorganic salts/PVP composite nano fiber;
(3) above-mentioned zinc gallium inorganic salts/PVP composite nano fiber is calcined, naturally cooled to room temperature, namely get zinc gallium composite oxides nanofiber;
(4) above-mentioned zinc gallium composite oxides nanofiber is placed mobile ammonia atmosphere nitrogenize, question response finishes to naturally cool to room temperature, obtains (Ga 1-xZn x) (N 1-xO x) nanofiber.
2. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: the volume ratio of ethanol and water is 1:1～9:1 in the mixed solution described in the step (1).
3. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: the zinc salt described in the step (1), the concentration of gallium salt in mixed solution are respectively 0.05～0.3mol/L.
4. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: the zinc salt described in the step (1) and gallium salt water soluble and ethanol, the mol ratio of zinc salt and gallium salt is 1:5～5:1.
5. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: the mass ratio of the zinc salt described in the step (1) and gallium salt sum and PVP is 1:2～2:1; The molecular weight of PVP is 30000-1300000.
6. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: the technological parameter of the electrostatic spinning described in the step (2) is: described gel is poured in the syringe, then described syringe is fixed on the miniflow pump, advancing speed is 5～30 μ L/min, nozzle is 10～20cm with the distance that receives aluminium foil or wire netting, add 10～20kV electrostatic field and carry out spinning between nozzle and reception aluminium foil or wire netting, ambient humidity control is 15%～25% during spinning.
7. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: heating rate is 2～8 ℃/min in the calcining described in the step (3), and calcining heat is 400～600 ℃, and temperature retention time is 3～6h.
8. a kind of method of electrostatic spinning according to claim 1 prepares (Ga 1-xZn x) (N 1-xO x) method of nanofiber, it is characterized in that: ammonia flow is 200～400mL/min in the ammonia atmosphere nitrogenize described in the step (4), and nitridation conditions is that heating rate is 2～8 ℃/min, and nitriding temperature is 400～845 ℃, and temperature retention time is 3～10h.
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CN114436322A (en) * 2022-03-02 2022-05-06 湖南师范大学 Gallium oxide nano material and preparation method and application thereof

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CN103878011A (en) * 2014-04-17 2014-06-25 哈尔滨工业大学 Method for synthesizing GaN: ZnO solid solution photocatalyst
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