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CN104383955A - Spherical g-C3N4-Bi1-xGdxVO4 composite photocatalyst and preparation method and application thereof - Google Patents

Spherical g-C3N4-Bi1-xGdxVO4 composite photocatalyst and preparation method and application thereof Download PDF

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CN104383955A
CN104383955A CN201410713101.3A CN201410713101A CN104383955A CN 104383955 A CN104383955 A CN 104383955A CN 201410713101 A CN201410713101 A CN 201410713101A CN 104383955 A CN104383955 A CN 104383955A
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CN104383955B (en
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谈国强
赵程程
任慧君
夏傲
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a spherical g-C3N4-Bi1-xGdxVO4 composite photocatalyst and a preparation method and an application of the spherical g-C3N4-Bi1-xGdxVO4 composite photocatalyst. According to the method, a bismuth salt solution and a vanadium salt solution are mixed according to a molar ratio of Bi:V=1:1, after the pH value is adjusted, a suspension formed by dispersing C3N4 into water and Gd(NO3)3.6H2O are added to form a precursor solution, and then a target product is prepared through microwave hydrothermal reaction. According to the spherical g-C3N4-Bi1-xGdxVO4 composite photocatalyst and the preparation method and the application, disclosed by the invention, g-C3N4 and BiVO4 are compounded by a microwave hydrothermal method, Gd is doped into the BiVO4, and the spherical g-C3N4-Bi1-xGdxVO4 composite photocatalyst is rapidly synthesized in one step, so that the method has the advantages of easiness in operation, mild conditions, short reaction time and the like, and the prepared composite photocatalyst has spherical morphology, large specific surface area, uniformly distributed particle size, and better photocatalytic performance, and can be used for degrading organic matter and environmental pollutants.

Description

A kind of spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst and its preparation method and application
Technical field
The invention belongs to field of functional materials, relate to a kind of spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst and its preparation method and application.
Background technology
In recent years, photocatalysis technology causes and pays close attention to widely in depollution of environment field, has that self is pollution-free, operating procedure is simple, directly by advantages such as sunshine light source utilizations, can have extraordinary development prospect, wherein with BiVO 4for a kind of Typical Representative.BiVO 4be the Yellow organic dye of the toxic element such as a kind of not leaded, chromium, it has good ferroelectricity and ionic conductivity simultaneously.In addition, the photochemical catalyst TiO that its energy gap is relatively traditional 2narrower (mainly contain cubic Zircon cut, monocline scheelite type and cubic scheelite type three kinds of crystal structures, corresponding energy gap is respectively 2.9eV, 2.4eV and 2.4eV), has good photocatalysis potential quality.In existing report, BiVO 4degradable material has, methylene blue, methyl orange, rhodamine B, eosin W or W S, acid Exocarpium Citri Rubrum, phenol, toluene (gas phase), 4-alkylphenol, 2, 4-dinitrophenol, polycyclic aromatic hydrocarbon, also has about BiVO in addition 4nO, associating deoxidization, degradation Cr (VI) phenol and the CO by reducing in liquid in air are removed in photocatalysis 2select the report generating ethanol etc.This shows, BiVO 4can with many kinds of substance generation redox reaction, almost non-selectivity, thus has higher application potential quality.
Hardness and the diamond of carbon-nitrogen material are suitable, common carbon-nitrogen material mainly comprises rare two kinds of the graphite of carbonitride and N doping, wherein carbonitride is again because its crystal formation had is different, and be divided into five types, be respectively α phase, β phase, Emission in Cubic, accurate Emission in Cubic and class graphite phase carbon nitride (g-C 3n 4), wherein with g-C 3n 4be most widely used.G-C 3n 4be a kind of typical polymer semiconductor, the C in its structure, atom N are with sp 2the pi-conjugated system of hydridization height of formation delocalization, its energy gap is 2.7eV, absorbing wavelength can be less than the light of 475nm, is a kind of continuable, photochemical catalyst that can utilize Visible Light Induced Photocatalytic pollutant, has very large application potential in photocatalysis field.In addition, due to the strong covalent bond formed between carbon atom and nitrogen-atoms, g-C is made 3n 4can in the water of pH=0 ~ 14 under light illumination retention properties stablize, the character of this excellence makes g-C 3n 4in photocatalytic process, there is very large application stability.But g-C 3n 4owing to being subject to the characteristic restriction of material itself, also there are some problems, as little in specific area, produce that the exciton binding energy of photo-generated carrier is high, photo-generate electron-hole compound is serious, quantum efficiency is low and energy gap is comparatively large and effectively can not utilize sunshine etc., seriously constrain its popularization in energy and environment field.
Up to now, microwave-hydrothermal method is utilized to prepare spherical g-C 3n 4-Bi 1-xgd xvO 4there is not been reported in the work of powder, also do not have patent and bibliographical information to cross the spherical g-C prepared by microwave-hydrothermal method 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
Summary of the invention
The object of the present invention is to provide a kind of spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst and its preparation method and application, its reaction time is short, and technological process is simple, and obtained powder specific-surface area detection is comparatively large, even particle size distribution and cost is lower.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of spherical g-C 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, comprises the following steps:
Step 1, by Bi (NO 3) 35H 2o is soluble in water, stirs, and obtains bismuth salting liquid, by NH 4vO 3be dissolved in hot water, heating is stirred to dissolves completely, obtains vanadic salts solution;
Step 2, mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, stirs, obtain mixed liquor; In mixed liquor, add mineralizer, the pH value regulating mixed liquor is 9.3 ~ 9.4, stirs, obtains mixed liquor A;
Step 3, by C 3n 4powder is scattered in water, stirs, and forms suspension; Suspension is added in mixed liquor A, stir, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is (5 ~ 40): (95 ~ 60);
Step 4, by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs, and forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is (4 ~ 8): (96 ~ 92);
Step 5, puts into microwave hydrothermal reaction kettle by precursor liquid, with the power of 300W, and microwave hydrothermal reaction 30 ~ 50min at 190 ~ 210 DEG C; Naturally cool to room temperature after having reacted, washing of precipitate reaction generated, drying, obtain spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
Bi (NO in described bismuth salting liquid 3) 35H 2the concentration of O is 0.4 ~ 0.6mol/L, NH in vanadic salts solution 4vO 3concentration be 0.4 ~ 0.6mol/L, the brown color that vanadic salts solution is transparent, containing precipitation.
Required time that stirs in described step 1 is 20 ~ 30min; The temperature of hot water is 80 ~ 90 DEG C, and heating is stirred to that to dissolve the required time be completely 10 ~ 15min, and heating-up temperature is 40 ~ 50 DEG C.
Mineralizer in described step 2 is the NaOH solution of 4 ~ 6mol/L.
Required time that stirs in described step 2, step 3 and step 4 is 20 ~ 30min.
C in described step 3 3n 4obtained through grinding after 3 ~ 4 hours in 550 ~ 600 DEG C of calcinings in atmosphere by melamine, its fineness is below 0.088mm;
C in suspension 3n 4concentration be 4.6 ~ 55.2g/L.
The packing ratio of described microwave hydrothermal reaction kettle is 50% ~ 65%.
Drying in described step 5 is dry 10 ~ 12h at 75 ~ 85 DEG C.
Spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst, its pattern is spherical, is g-C 3n 4and Bi 1-xgd xvO 4mixed powder, wherein g-C 3n 4with Bi 1-xgd xvO 4mol ratio be (5 ~ 60): (95 ~ 40), Bi 1-xgd xvO 4for Tetragonal, space structure group is I41/admz, x=0.04 ~ 0.08, g-C 3n 4be six side's phases, space structure group is P3.
Spherical g-C 3n 4-Bi 1-xgd xvO 4the application of composite photo-catalyst in degraded environmental contaminants and organic matter.
Compared with prior art, the present invention has following beneficial effect:
Spherical g-C provided by the invention 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, with Bi (NO 3) 35H 2o is Bi source, with NH 4vO 3for V source, bismuth salting liquid and vanadic salts solution are mixed and adjust ph according to the mol ratio of Bi:V=1:1, then will be dispersed with C 3n 4suspension and Gd (NO 3) 36H 2o adds in mixed liquor, stirs and forms precursor liquid, then carry out microwave hydrothermal reaction, obtain spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.The present invention by microwave-hydrothermal method by g-C 3n 4with BiVO 4carry out compound, and Gd is doped into BiVO 4in, the spherical g-C of a step Fast back-projection algorithm 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.The method combines the heat characteristic of microwave uniqueness and the advantage of hydro-thermal method, have that flow process is few, simple to operate, cheaper starting materials is easy to get, reaction speed is fast, generated time is short, reaction condition is gentle, reaction efficiency is high, environmental friendliness, technique are simple and easy to control, manufacturing cycle is short, save the energy, obtained product has the features such as higher purity, narrow domain size distribution and homogeneous form.
Spherical g-C provided by the invention 3n 4-Bi 1-xgd xvO 4composite photo-catalyst is g-C 3n 4and Bi 1-xgd xvO 4mixed powder, wherein g-C 3n 4with Bi 1-xgd xvO 4mol ratio be (5 ~ 60): (95 ~ 40), Bi 1-xgd xvO 4for Tetragonal, space structure group is I41/admz, x=0.04 ~ 0.08, g-C 3n 4be six side's phases, space structure group is P3.This composite photo-catalyst has the spherical shape pattern assembled by single-size, and specific area is large, and even particle size distribution, ball particle diameter is along with C 3n 4being on the increase of content and reducing, and domain size distribution is more and more narrow.Spherical g-C provided by the invention 3n 4-Bi 1-xgd xvO 4composite photo-catalyst can be good at C 3n 4and BiVO 4advantage carry out complementation, through photocatalysis test, prove spherical g-C provided by the invention 3n 4-Bi 1-xgd xvO 4composite photo-catalyst has good photocatalysis performance, can be used in degradation of organic substances, has a good application prospect, and expands its promoting the use of in energy and environment field.
Accompanying drawing explanation
Fig. 1 is spherical g-C prepared by the embodiment of the present invention 1 3n 4-Bi 1-xgd xvO 4the XRD figure of composite photo-catalyst;
Fig. 2 is spherical g-C prepared by the embodiment of the present invention 1 3n 4-Bi 1-xgd xvO 4the FT-IR infrared spectrogram of composite photo-catalyst;
Fig. 3 is spherical g-C prepared by the embodiment of the present invention 1 3n 4-Bi 1-xgd xvO 4the SEM figure of composite photo-catalyst, wherein the magnification ratio of (a) is 2000 times, and the magnification ratio of (b) is 15000 times;
Fig. 4 is spherical g-C prepared by the embodiment of the present invention 1 3n 4-Bi 1-xgd xvO 4the absorbance change curve of the rhodamine B degradation of composite photo-catalyst.
Detailed description of the invention
Be described further below in conjunction with accompanying drawing and the preferred specific embodiment the present invention of the present invention, it is pure that raw material is analysis.
Embodiment 1:
Step 1: by 0.01mol Bi (NO 3) 35H 2o is dissolved in 20ml deionized water, under room temperature, magnetic stirring apparatus stirring 30min to stirring, obtaining Bi (NO 3) 35H 2o concentration is the bismuth salting liquid of 0.5mol/L; By 0.01mol NH 4vO 3be dissolved in the 20ml deionized water of 85 DEG C, magnetic stirring apparatus stir 13min with the heating temperatures of 45 DEG C, to the transparent brown color of vanadic salts solution, obtains NH 4vO 3concentration is the vanadic salts solution of 0.5mol/L, and it is long that attention can not heat mixing time, and causes occurring that yellow mercury oxide (will there will be an other phase V if there is precipitation 2o 5).
Step 2: that step 1 is prepared mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, magnetic stirring apparatus stirs 30min to stirring, obtain mixed liquor, then in mixed liquor, add 5ml concentration is that the NaOH solution of 5mol/L is as mineralizer, the pH value regulating mixed liquor is 9.3, then on magnetic stirring apparatus, 30min is stirred, obtained mixed liquor A; Notice that NaOH solution is when preparing, and should use the NaOH reagent of sheet drying, can not use graininess NaOH, to prevent the NaOH solution alkalescence instability prepared.
Step 3: by C 3n 4powder is scattered in 10mL water, stirs 20min, forms suspension, C in suspension 3n 4concentration be 18.4g/L; Suspension is added in mixed liquor A, stir 30min, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is 17:83; Wherein C 3n 4with melamine (C 3h 6n 6) 600 DEG C of calcinings 3 hours are obtained in atmosphere, present faint yellow caking after calcining, needing to be ground to fineness is below 0.088mm;
Step 4: by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs 30min, forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is 6:94;
Step 5: presoma is put into teflon-lined microwave hydrothermal reaction kettle, and rinse by 5mL deionized water, the packing ratio controlling microwave hydrothermal reaction kettle is 60%, sealing microwave hydrothermal reaction kettle; Microwave hydrothermal hydrothermal reaction kettle is put into microwave hydrothermal reaction, and setting microwave hydrothermal reaction temperature is 200 DEG C, and temperature retention time is 40min, and power is 300W; Naturally cool to room temperature after question response completes, the precipitation in taking-up reactor, spends deionized water and absolute ethyl alcohol respectively washs 3 times, and finally dry 12h in 80 DEG C of non-airtight isoperibols, obtains spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
The thing phase composition of the product obtained by XRD determining embodiment 1, as can be seen from Figure 1 adopts the spherical g-C that microwave-hydrothermal method can be prepared 3n 4-Bi 1-xgd xvO 4composite photo-catalyst is Tetragonal BiVO 4(JCPDS NO.14-0133), space structure group is I41/admz, is that six side phase C have appearred in 28.154 ° of places in the angle of diffraction 3n 4(JCPDS NO.52-0780), diffraction maximum space structure group is P3.
Fig. 2 is the spherical g-C that embodiment 1 obtains 3n 4-Bi 1-xgd xvO 4the FT-IR infrared spectrogram of composite photo-catalyst, it is at 3400cm -1, 1200-1600cm -1and 750cm -1there is the absorption band that three strong, by the BiVO of itself and pure phase 4with pure phase C 3n 4infared spectrum contrast can determine, 3400cm- 1the broad absorption band at place is hydrogen bonds district, with NH 2group, NH group and BiVO 4the stretching vibration of the OH group of adsorbed water is relevant, 1200-1600cm -1absorption band and typical aroma type synthesize (C 3n 3and C 6n 7) stretching vibration and the flexural vibrations of adsorbed water relevant, 750cm -1absworption peak then with VO 4 3-stretching vibration is relevant.
Fig. 3 is the spherical g-C that embodiment 1 obtains 3n 4-Bi 1-xgd xvO 4the SEM figure of composite photo-catalyst, as can be seen from the figure, obtained g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst is even spherical shape structure.
Fig. 4 is the spherical g-C that embodiment 1 obtains 3n 4-Bi 1-xgd xvO 4the absorbance change curve of composite photo-catalyst rhodamine B degradation solution under ultraviolet light, degrades 89.69%, illustrates that it has good photocatalysis performance, can be used in degradation of organic substances and environmental contaminants in 25min.
Embodiment 2:
Step 1: by Bi (NO 3) 35H 2o is dissolved in 20ml deionized water, under room temperature, magnetic stirring apparatus stirring 20min to stirring, obtaining Bi (NO 3) 35H 2o concentration is the bismuth salting liquid of 0.4mol/L; By NH 4vO 3be dissolved in the 20ml deionized water of 80 DEG C, magnetic stirring apparatus stir 11min with the heating temperatures of 40 DEG C, to the transparent brown color of vanadic salts solution, obtains NH 4vO 3concentration is the vanadic salts solution of 0.4mol/L, and it is long that attention can not heat mixing time, and cause occurring yellow mercury oxide.
Step 2: that step 1 is prepared mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, magnetic stirring apparatus stirs 20min to stirring, obtain mixed liquor, then in mixed liquor, add concentration is that the NaOH solution of 4mol/L is as mineralizer, the pH value regulating mixed liquor is 9.4, then on magnetic stirring apparatus, 20min is stirred, obtained mixed liquor A; Notice that NaOH solution is when preparing, and should use the NaOH reagent of sheet drying, can not use graininess NaOH, to prevent the NaOH solution alkalescence instability prepared.
Step 3: by C 3n 4powder is scattered in 10mL water, stirs 30min, forms suspension, C in suspension 3n 4concentration be 4.6g/L; Suspension is added in mixed liquor A, stir 20min, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is 5:95; Wherein C 3n 4with melamine (C 3h 6n 6) 550 DEG C of calcinings 4 hours are obtained in atmosphere, present faint yellow caking after calcining, needing to be ground to fineness is below 0.088mm;
Step 4: by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs 20min, forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is 4:96;
Step 5: presoma is put into teflon-lined microwave hydrothermal reaction kettle, and rinse by 5mL deionized water, the packing ratio controlling microwave hydrothermal reaction kettle is 65%, sealing microwave hydrothermal reaction kettle; Microwave hydrothermal hydrothermal reaction kettle is put into microwave hydrothermal reaction, and setting microwave hydrothermal reaction temperature is 210 DEG C, and temperature retention time is 30min, and power is 300W; Naturally cool to room temperature after question response completes, the precipitation in taking-up reactor, spends deionized water and absolute ethyl alcohol respectively washs 3 times, and finally dry 11h in 75 DEG C of non-airtight isoperibols, obtains spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
Embodiment 3:
Step 1: by Bi (NO 3) 35H 2o is dissolved in 20ml deionized water, under room temperature, magnetic stirring apparatus stirring 25min to stirring, obtaining Bi (NO 3) 35H 2o concentration is the bismuth salting liquid of 0.6mol/L; By NH 4vO 3be dissolved in the 20ml deionized water of 90 DEG C, magnetic stirring apparatus stir 10min with the heating temperatures of 50 DEG C, to the transparent brown color of vanadic salts solution, obtains NH 4vO 3concentration is the vanadic salts solution of 0.6mol/L, and it is long that attention can not heat mixing time, and cause occurring yellow mercury oxide.
Step 2: that step 1 is prepared mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, magnetic stirring apparatus stirs 25min to stirring, obtain mixed liquor, then in mixed liquor, add concentration is that the NaOH solution of 6mol/L is as mineralizer, the pH value regulating mixed liquor is 9.35, then on magnetic stirring apparatus, 25min is stirred, obtained mixed liquor A; Notice that NaOH solution is when preparing, and should use the NaOH reagent of sheet drying, can not use graininess NaOH, to prevent the NaOH solution alkalescence instability prepared.
Step 3: by C 3n 4powder is scattered in 10mL water, stirs 25min, forms suspension, C in suspension 3n 4concentration be 55.2g/L; Suspension is added in mixed liquor A, stir 25min, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is 40:60; Wherein C 3n 4with melamine (C 3h 6n 6) 580 DEG C of calcinings 3.5 hours are obtained in atmosphere, present faint yellow caking after calcining, needing to be ground to fineness is below 0.088mm;
Step 4: by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs 25min, forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is 8:92;
Step 5: presoma is put into teflon-lined microwave hydrothermal reaction kettle, and rinse by 5mL deionized water, the packing ratio controlling microwave hydrothermal reaction kettle is 50%, sealing microwave hydrothermal reaction kettle; Microwave hydrothermal hydrothermal reaction kettle is put into microwave hydrothermal reaction, and setting microwave hydrothermal reaction temperature is 190 DEG C, and temperature retention time is 50min, and power is 300W; Naturally cool to room temperature after question response completes, the precipitation in taking-up reactor, spends deionized water and absolute ethyl alcohol respectively washs 3 times, and finally dry 10h in 85 DEG C of non-airtight isoperibols, obtains spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
Embodiment 4:
Step 1: by Bi (NO 3) 35H 2o is dissolved in 20ml deionized water, under room temperature, magnetic stirring apparatus stirring 22min to stirring, obtaining Bi (NO 3) 35H 2o concentration is the bismuth salting liquid of 0.45mol/L; By NH 4vO 3be dissolved in the 20ml deionized water of 82 DEG C, magnetic stirring apparatus stir 15min with the heating temperatures of 42 DEG C, to the transparent brown color of vanadic salts solution, obtains NH 4vO 3concentration is the vanadic salts solution of 0.45mol/L, and it is long that attention can not heat mixing time, and cause occurring yellow mercury oxide.
Step 2: that step 1 is prepared mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, magnetic stirring apparatus stirs 22min to stirring, obtain mixed liquor, then in mixed liquor, add concentration is that the NaOH solution of 4.5mol/L is as mineralizer, the pH value regulating mixed liquor is 9.32, then on magnetic stirring apparatus, 22min is stirred, obtained mixed liquor A; Notice that NaOH solution is when preparing, and should use the NaOH reagent of sheet drying, can not use graininess NaOH, to prevent the NaOH solution alkalescence instability prepared.
Step 3: by C 3n 4powder is scattered in 10mL water, stirs 22min, forms suspension, C in suspension 3n 4concentration be 36.8g/L; Suspension is added in mixed liquor A, stir 22min, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is 29:71; Wherein C 3n 4with melamine (C 3h 6n 6) 550 DEG C of calcinings 4 hours are obtained in atmosphere, present faint yellow caking after calcining, needing to be ground to fineness is below 0.088mm;
Step 4: by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs 22min, forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is 5:95;
Step 5: presoma is put into teflon-lined microwave hydrothermal reaction kettle, and rinse by 5mL deionized water, the packing ratio controlling microwave hydrothermal reaction kettle is 55%, sealing microwave hydrothermal reaction kettle; Microwave hydrothermal hydrothermal reaction kettle is put into microwave hydrothermal reaction, and setting microwave hydrothermal reaction temperature is 195 DEG C, and temperature retention time is 45min, and power is 300W; Naturally cool to room temperature after question response completes, the precipitation in taking-up reactor, spends deionized water and absolute ethyl alcohol respectively washs 3 times, and finally dry 11.5h in 78 DEG C of non-airtight isoperibols, obtains spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
Embodiment 5
Step 1: by Bi (NO 3) 35H 2o is dissolved in 20ml deionized water, under room temperature, magnetic stirring apparatus stirring 28min to stirring, obtaining Bi (NO 3) 35H 2o concentration is the bismuth salting liquid of 0.55mol/L; By NH 4vO 3be dissolved in the 20ml deionized water of 88 DEG C, magnetic stirring apparatus stir 12min with the heating temperatures of 48 DEG C, to the transparent brown color of vanadic salts solution, obtains NH 4vO 3concentration is the vanadic salts solution of 0.55mol/L, and it is long that attention can not heat mixing time, and cause occurring yellow mercury oxide.
Step 2: that step 1 is prepared mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, magnetic stirring apparatus stirs 28min to stirring, obtain mixed liquor, then in mixed liquor, add concentration is that the NaOH solution of 5.5mol/L is as mineralizer, the pH value regulating mixed liquor is 9.37, then on magnetic stirring apparatus, 28min is stirred, obtained mixed liquor A; Notice that NaOH solution is when preparing, and should use the NaOH reagent of sheet drying, can not use graininess NaOH, to prevent the NaOH solution alkalescence instability prepared.
Step 3: by C 3n 4powder is scattered in 10mL water, stirs 28min, forms suspension, C in suspension 3n 4concentration be 27.6g/L; Suspension is added in mixed liquor A, stir 28min, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is 23:77; Wherein C 3n 4with melamine (C 3h 6n 6) 600 DEG C of calcinings 3 hours are obtained in atmosphere, present faint yellow caking after calcining, needing to be ground to fineness is below 0.088mm;
Step 4: by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs 28min, forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is 7:93;
Step 5: presoma is put into teflon-lined microwave hydrothermal reaction kettle, and rinse by 5mL deionized water, the packing ratio controlling microwave hydrothermal reaction kettle is 58%, sealing microwave hydrothermal reaction kettle; Microwave hydrothermal hydrothermal reaction kettle is put into microwave hydrothermal reaction, and setting microwave hydrothermal reaction temperature is 205 DEG C, and temperature retention time is 35min, and power is 300W; Naturally cool to room temperature after question response completes, the precipitation in taking-up reactor, spends deionized water and absolute ethyl alcohol respectively washs 3 times, and finally dry 10.5h in 82 DEG C of non-airtight isoperibols, obtains spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
Embodiment 6
Step 1: by 0.01mol Bi (NO 3) 35H 2o is dissolved in 20ml deionized water, under room temperature, magnetic stirring apparatus stirring 30min to stirring, obtaining Bi (NO 3) 35H 2o concentration is the bismuth salting liquid of 0.5mol/L; By 0.01mol NH 4vO 3be dissolved in the 20ml deionized water of 85 DEG C, magnetic stirring apparatus stir 14min with the heating temperatures of 45 DEG C, to the transparent brown color of vanadic salts solution, obtains NH 4vO 3concentration is the vanadic salts solution of 0.5mol/L, and it is long that attention can not heat mixing time, and cause occurring yellow mercury oxide.
Step 2: that step 1 is prepared mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, magnetic stirring apparatus stirs 30min to stirring, obtain mixed liquor, then in mixed liquor, add concentration is that the NaOH solution of 5mol/L is as mineralizer, the pH value regulating mixed liquor is 9.38, then on magnetic stirring apparatus, 30min is stirred, obtained mixed liquor A; Notice that NaOH solution is when preparing, and should use the NaOH reagent of sheet drying, can not use graininess NaOH, to prevent the NaOH solution alkalescence instability prepared.
Step 3: by C 3n 4powder is scattered in 10mL water, stirs 20min, forms suspension, C in suspension 3n 4concentration be 11.04g/L; Suspension is added in mixed liquor A, stir 30min, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is 11:89; Wherein C 3n 4with melamine (C 3h 6n 6) 570 DEG C of calcinings 3.5 hours are obtained in atmosphere, present faint yellow caking after calcining, needing to be ground to fineness is below 0.088mm;
Step 4: by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs 30min, forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is 6:94;
Step 5: presoma is put into teflon-lined microwave hydrothermal reaction kettle, and rinse by 5mL deionized water, the packing ratio controlling microwave hydrothermal reaction kettle is 62%, sealing microwave hydrothermal reaction kettle; Microwave hydrothermal hydrothermal reaction kettle is put into microwave hydrothermal reaction, and setting microwave hydrothermal reaction temperature is 200 DEG C, and temperature retention time is 40min, and power is 300W; Naturally cool to room temperature after question response completes, the precipitation in taking-up reactor, spends deionized water and absolute ethyl alcohol respectively washs 3 times, and finally dry 12h in 80 DEG C of non-airtight isoperibols, obtains spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
The spherical g-C that the present invention obtains 3n 4-Bi 1-xgd xvO 4composite photo-catalyst is g-C 3n 4and Bi 1-xgd xvO 4mixed powder, wherein g-C 3n 4with Bi 1-xgd xvO 4mol ratio be (5 ~ 60): (95 ~ 40), Bi 1-xgd xvO 4for Tetragonal, space structure group is I41/admz, x=0.04 ~ 0.08, g-C 3n 4be six side's phases, space structure group is P3.This composite photo-catalyst has the spherical shape pattern assembled by single-size, and specific area is large, and even particle size distribution, ball particle diameter is along with C 3n 4being on the increase of content and reducing, and domain size distribution is more and more narrow.Spherical g-C provided by the invention 3n 4-Bi 1-xgd xvO 4composite photo-catalyst can be good at C 3n 4and BiVO 4advantage carry out complementation, through photocatalysis test, prove spherical g-C provided by the invention 3n 4-Bi 1-xgd xvO 4composite photo-catalyst has good photocatalysis performance, can be used in degradation of organic substances, has a good application prospect.
For the foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading description of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.

Claims (10)

1. a spherical g-C 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that, comprises the following steps:
Step 1, by Bi (NO 3) 35H 2o is soluble in water, stirs, and obtains bismuth salting liquid, by NH 4vO 3be dissolved in hot water, heating is stirred to dissolves completely, obtains vanadic salts solution;
Step 2, mixes bismuth salting liquid and vanadic salts solution according to the mol ratio of Bi:V=1:1, stirs, obtain mixed liquor; In mixed liquor, add mineralizer, the pH value regulating mixed liquor is 9.3 ~ 9.4, stirs, obtains mixed liquor A;
Step 3, by C 3n 4powder is scattered in water, stirs, and forms suspension; Suspension is added in mixed liquor A, stir, obtain mixed liquid B, C in mixed liquid B 3n 4with Bi (NO 3) 35H 2the mol ratio of O is (5 ~ 40): (95 ~ 60);
Step 4, by Gd (NO 3) 36H 2o adds in mixed liquid B, stirs, and forms precursor liquid; Gd (NO in precursor liquid 3) 36H 2o and Bi (NO 3) 35H 2the mol ratio of O is (4 ~ 8): (96 ~ 92);
Step 5, puts into microwave hydrothermal reaction kettle by precursor liquid, with the power of 300W, and microwave hydrothermal reaction 30 ~ 50min at 190 ~ 210 DEG C; Naturally cool to room temperature after having reacted, washing of precipitate reaction generated, drying, obtain spherical g-C 3n 4-Bi 1-xgd xvO 4composite photo-catalyst.
2. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: Bi (NO in described bismuth salting liquid 3) 35H 2the concentration of O is 0.4 ~ 0.6mol/L, NH in vanadic salts solution 4vO 3concentration be 0.4 ~ 0.6mol/L, the brown color that vanadic salts solution is transparent, containing precipitation.
3. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: the required time that stirs in described step 1 is 20 ~ 30min; The temperature of hot water is 80 ~ 90 DEG C, and heating is stirred to that to dissolve the required time be completely 10 ~ 15min, and heating-up temperature is 40 ~ 50 DEG C.
4. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: the mineralizer in described step 2 is the NaOH solution of 4 ~ 6mol/L.
5. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: the required time that stirs in described step 2, step 3 and step 4 is 20 ~ 30min.
6. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: C in described step 3 3n 4obtained through grinding after 3 ~ 4 hours in 550 ~ 600 DEG C of calcinings in atmosphere by melamine, its fineness is below 0.088mm;
C in suspension 3n 4concentration be 4.6 ~ 55.2g/L.
7. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: the packing ratio of described microwave hydrothermal reaction kettle is 50% ~ 65%.
8. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the preparation method of composite photo-catalyst, is characterized in that: the drying in described step 5 is 10 ~ 12h dry at 75 ~ 85 DEG C.
9. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the spherical g-C that the preparation method of composite photo-catalyst obtains 3n 4-Bi 1-xgd xvO 4composite photo-catalyst, is characterized in that: its pattern is spherical, is g-C 3n 4and Bi 1-xgd xvO 4mixed powder, wherein g-C 3n 4with Bi 1-xgd xvO 4mol ratio be (5 ~ 60): (95 ~ 40), Bi 1-xgd xvO 4for Tetragonal, space structure group is I41/admz, x=0.04 ~ 0.08, g-C 3n 4be six side's phases, space structure group is P3.
10. spherical g-C according to claim 1 3n 4-Bi 1-xgd xvO 4the spherical g-C that the preparation method of composite photo-catalyst obtains 3n 4-Bi 1-xgd xvO 4the application of composite photo-catalyst in degraded environmental contaminants and organic matter.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105597820A (en) * 2015-12-24 2016-05-25 西北师范大学 Graphite phase-like carbon nitride/tetracarboxylphenylporphyrin nano-composite material and preparation method therefor
CN109999786A (en) * 2019-03-20 2019-07-12 中南林业科技大学 A kind of semiconductor light-catalyst and its preparation method and application
CN110656350A (en) * 2019-11-13 2020-01-07 苏州大学 Ferroelectric film ternary composite photoelectrode and preparation method thereof
CN112058291A (en) * 2020-07-22 2020-12-11 上海应用技术大学 Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050214199A1 (en) * 2002-07-26 2005-09-29 Sued-Chemie Catalysts Japan, Inc Manganese compound, process for producing the same, and method of utilization of the same
CN103433023A (en) * 2013-08-15 2013-12-11 陕西科技大学 Gd-doped BiVO4 photocatalyst as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050214199A1 (en) * 2002-07-26 2005-09-29 Sued-Chemie Catalysts Japan, Inc Manganese compound, process for producing the same, and method of utilization of the same
CN103433023A (en) * 2013-08-15 2013-12-11 陕西科技大学 Gd-doped BiVO4 photocatalyst as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MANOU等: "Synthesis and characterization of g-C3N4/BiVO4 composite photocatalysts with improved visible-light-driven photocatalytic performance", 《J SOL-GEL SCI TECHNOL》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105597820A (en) * 2015-12-24 2016-05-25 西北师范大学 Graphite phase-like carbon nitride/tetracarboxylphenylporphyrin nano-composite material and preparation method therefor
CN105597820B (en) * 2015-12-24 2018-02-16 西北师范大学 The carbonitride of one species graphite-phase/tetracarboxylic phenyl porphyrin nano composite and preparation method thereof
CN109999786A (en) * 2019-03-20 2019-07-12 中南林业科技大学 A kind of semiconductor light-catalyst and its preparation method and application
CN110656350A (en) * 2019-11-13 2020-01-07 苏州大学 Ferroelectric film ternary composite photoelectrode and preparation method thereof
CN110656350B (en) * 2019-11-13 2021-11-19 苏州大学 Ferroelectric film ternary composite photoelectrode and preparation method thereof
CN112058291A (en) * 2020-07-22 2020-12-11 上海应用技术大学 Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof

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