CN104383955B - A kind of spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst and its preparation method and application - Google Patents
A kind of spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst and its preparation method and application, the method according to the mixed in molar ratio of Bi:V=1:1, adds bismuth salting liquid and vanadic salts solution by C after regulating pH value3N4Be dispersed in water suspension and the Gd (NO of formation3)3·6H2O, forms precursor liquid, then is reacted and made target product by microwave hydrothermal. The present invention by microwave-hydrothermal method by g-C3N4With BiVO4Carry out compoundly, and Gd is doped into BiVO4In, a step has been synthesized spherical g-C fast3N4-Bi1-xGdxVO4Composite photo-catalyst, have simple to operate, mild condition, the advantages such as the reaction time is short, the composite photo-catalyst making is spherical shape pattern, specific area is large, even particle size distribution, has good photocatalysis performance, can be used in degradation of organic substances and environmental contaminants.
Description
Technical field
The invention belongs to field of functional materials, relate to a kind of spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst and its preparation method and application.
Background technology
In recent years, photocatalysis technology has caused widely in depollution of environment field to be paid close attention to, and has that self is pollution-free, operating procedure simple, can, directly by advantages such as sunshine light source utilizations, have extraordinary development prospect, wherein with BiVO4For a kind of Typical Representative. BiVO4Be the Yellow organic dye of the poisonous elements 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 traditional2Narrower (mainly contain cubic Zircon cut, monocline scheelite type and three kinds of crystal structures of cubic scheelite type, corresponding energy gap is respectively 2.9eV, 2.4eV and 2.4eV), has good photocatalysis potential quality. In existing report, BiVO4Degradable material has, and 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 have in addition about BiVO4Photocatalysis is removed airborne NO, associating deoxidization, degradation Cr (VI) phenol and is passed through the CO in reduction liquid2The report of selection generation ethanol etc. This shows BiVO4Can with many kinds of substance generation redox reaction, almost non-selectivity, thereby there is 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 nitrogen doping, wherein carbonitride is again because of its crystal formation difference having, and be divided into five types, be respectively α phase, β phase, Emission in Cubic, accurate Emission in Cubic and class graphite-phase carbonitride (g-C3N4), wherein with g-C3N4Be most widely used. g-C3N4Be a kind of typical polymer semiconductor, C in its structure, N atom are with sp2The pi-conjugated system of hydridization height of formation delocalization, its energy gap is 2.7eV, can absorbing wavelength 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 forming between carbon atom and nitrogen-atoms, make g-C3N4Can be in the water of pH=0～14 under illumination retention properties stable, the character of this excellence makes g-C3N4In photocatalytic process, there is very large application stability. But g-C3N4Owing to being subject to the characteristic limitations of material itself, also exist some problems, as little in specific area, produce that the exciton binding energy of photo-generated carrier is high, light induced electron-hole-recombination is serious, quantum efficiency is low and energy gap compared with large and can not effectively utilize sunshine etc., seriously restricted its popularization in energy and environment field.
Up to now, utilize microwave-hydrothermal method to prepare spherical g-C3N4-Bi1-xGdxVO4The work of powder there is not yet report, the spherical g-C that does not also have patent and bibliographical information to cross to prepare by microwave-hydrothermal method3N4-Bi1-xGdxVO4Composite photo-catalyst.
Summary of the invention
The object of the present invention is to provide a kind of spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst and its preparation method and application, its reaction time is short, and technological process is simple, and the powder specific-surface area detection making is larger, and even particle size distribution and cost are lower.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of spherical g-C3N4-Bi1-xGdxVO4The preparation method of composite photo-catalyst, comprises the following steps:
Step 1, by Bi (NO3)3·5H2O is soluble in water, stirs, and obtains bismuth salting liquid, by NH4VO3Be dissolved in hot water, heating is stirred to completely dissolves, and obtains vanadic salts solution;
Step 2, mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, stir, and obtains mixed liquor; In mixed liquor, add mineralizer, regulating the pH value of mixed liquor is 9.3～9.4, stirs, and obtains mixed liquor A;
Step 3, by C3N4Powder is scattered in water, stirs, and forms suspension; Suspension is added in mixed liquor A, stir, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is (5～40): (95～60);
Step 4, by Gd (NO3)3·6H2O adds in mixed liquid B, stirs, and forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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; After having reacted, naturally cool to room temperature, by the washing of precipitate of reaction generation, dry, obtain sphericalg-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
Bi (NO in described bismuth salting liquid3)3·5H2The concentration of O is 0.4～0.6mol/L, NH in vanadic salts solution4VO3Concentration be 0.4～0.6mol/L, vanadic salts solution is transparent brown color, does not contain 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 33N4Melamine is obtained through grinding after 3～4 hours in 550～600 DEG C of calcinings in air, and its fineness is below 0.088mm;
C in suspension3N4Concentration be 4.6～55.2g/L.
The packing ratio of described microwave hydrothermal reaction kettle is 50%～65%.
Being dried as dry 10～12h at 75～85 DEG C in described step 5.
Spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst, its pattern is spherical, is g-C3N4And Bi1-xGdxVO4Mixed powder, wherein g-C3N4With Bi1-xGdxVO4Mol ratio be (5～60): (95～40), Bi1-xGdxVO4For Tetragonal, space structure group is I41/admz, x=0.04～0.08, g-C3N4Be six side's phases, space structure group is P3.
Spherical g-C3N4-Bi1-xGdxVO4The application of composite photo-catalyst aspect degraded environmental contaminants and organic matter.
Compared with prior art, the present invention has following beneficial effect:
Spherical g-C provided by the invention3N4-Bi1-xGdxVO4The preparation method of composite photo-catalyst, with Bi (NO3)3·5H2O is Bi source, with NH4VO3For V source, bismuth salting liquid and vanadic salts solution are mixed according to a mole proportioning of Bi:V=1:1 and regulate pH value, then will be dispersed with C3N4Suspension and Gd (NO3)3·6H2O adds in mixed liquor, stirs and forms precursor liquid, then carry out microwave hydrothermal reaction, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst. The present invention by microwave-hydrothermal method by g-C3N4With BiVO4Carry out compoundly, and Gd is doped into BiVO4In, a step has been synthesized spherical g-C fast3N4-Bi1-xGdxVO4Composite 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, raw material is cheap and easy to get, reaction speed is fast, generated time is short, reaction condition is gentle, reaction efficiency is high, environmental friendliness, technique is simple and easy to control, manufacturing cycle is short, save the energy, the product making has that higher purity, narrow particle diameter distribute and the feature such as the form of homogeneous.
Spherical g-C provided by the invention3N4-Bi1-xGdxVO4Composite photo-catalyst is g-C3N4And Bi1-xGdxVO4Mixed powder, wherein g-C3N4With Bi1-xGdxVO4Mol ratio be (5～60): (95～40), Bi1-xGdxVO4For Tetragonal, space structure group is I41/admz, x=0.04～0.08, g-C3N4Be six side's phases, space structure group is P3. This composite photo-catalyst has the spherical shape pattern being assembled by single-size, and specific area is large, even particle size distribution, and ball particle diameter is along with C3N4Being on the increase of content and reducing, and particle diameter distributes more and more narrow. Spherical g-C provided by the invention3N4-Bi1-xGdxVO4Composite photo-catalyst can be good at C3N4And BiVO4Advantage carry out complementation, through photocatalysis test, prove spherical g-C provided by the invention3N4-Bi1-xGdxVO4Composite photo-catalyst has good photocatalysis performance, can be used in degradation of organic substances, has a good application prospect, and has expanded its promoting the use of in energy and environment field.
Brief description of the drawings
Fig. 1 is spherical g-C prepared by the embodiment of the present invention 13N4-Bi1-xGdxVO4The XRD figure of composite photo-catalyst;
Fig. 2 is spherical g-C prepared by the embodiment of the present invention 13N4-Bi1-xGdxVO4The FT-IR infrared spectrogram of composite photo-catalyst;
Fig. 3 is spherical g-C prepared by the embodiment of the present invention 13N4-Bi1-xGdxVO4The SEM figure of composite photo-catalyst, wherein the magnification ratio of (a) is 2000 times, magnification ratio (b) is 15000 times;
Fig. 4 is spherical g-C prepared by the embodiment of the present invention 13N4-Bi1-xGdxVO4The 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 0.01molBi (NO3)3·5H2O is dissolved in 20ml deionized water, under room temperature, stirs 30min to stirring on magnetic stirring apparatus, obtains Bi (NO3)3·5H2O concentration is the bismuth salting liquid of 0.5mol/L; By 0.01molNH4VO3Be dissolved in the 20ml deionized water of 85 DEG C, on magnetic stirring apparatus, add thermal agitation 13min with the temperature of 45 DEG C, be transparent brown color to vanadic salts solution, obtain NH4VO3Concentration is the vanadic salts solution of 0.5mol/L, and it is long that attention can not be heated mixing time, and causes occurring that yellow mercury oxide (will there will be an other phase V if there is precipitation2O5)。
Step 2: prepared by step 1 mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, on magnetic stirring apparatus, stir 30min to stirring, obtain mixed liquor, then be that the NaOH solution of 5mol/L is as mineralizer to adding 5ml concentration in mixed liquor, regulating the pH value of mixed liquor is 9.3, then on magnetic stirring apparatus, stir 30min, make mixed liquor A; Notice that NaOH solution, in the time of preparation, should use the dry NaOH reagent of sheet, can not use graininess NaOH, unstable to prevent the NaOH solution alkalescence of preparation.
Step 3: by C3N4Powder is scattered in 10mL water, stirs 20min, forms suspension, C in suspension3N4Concentration be 18.4g/L; Suspension is added in mixed liquor A, stir 30min, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is 17:83; Wherein C3N4With melamine (C3H6N6) in air 600 DEG C of calcinings within 3 hours, make, after calcining, present faint yellow caking, need to be ground to fineness be below 0.088mm;
Step 4: by Gd (NO3)3·6H2O adds in mixed liquid B, stirs 30min, forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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 of 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; After question response completes, naturally cool to room temperature, take out the precipitation in reactor, respectively wash 3 times with deionized water washing and absolute ethyl alcohol, finally dry 12h in 80 DEG C of non-airtight isoperibols, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
The thing phase composition of the product making with XRD determining embodiment 1, the spherical g-C that as can be seen from Figure 1 adopts microwave-hydrothermal method to prepare3N4-Bi1-xGdxVO4Composite photo-catalyst is Tetragonal BiVO4(JCPDSNO.14-0133), space structure group is I41/admz, is 28.154 ° locates to have occurred six side's phase C in the angle of diffraction3N4(JCPDSNO.52-0780), diffraction maximum space structure group is P3.
Fig. 2 is the spherical g-C that embodiment 1 makes3N4-Bi1-xGdxVO4The FT-IR infrared spectrogram of composite photo-catalyst, it is at 3400cm-1、1200-1600cm-1And 750cm-1There are three strong absorption bands, by the BiVO of itself and pure phase4With pure phase C3N4Infared spectrum contrast can determine, 3400cm-1The broad absorption band at place is hydrogen bonds district, with NH2Group, NH group and BiVO4The stretching vibration of the OH group of adsorbed water is relevant, 1200-1600cm-1Absorption band and typical aroma type synthesize (C3N3And C6N7) stretching vibration and the flexural vibrations of adsorbed water relevant, 750cm-1Absworption peak with VO4 3-Stretching vibration is relevant.
Fig. 3 is the spherical g-C that embodiment 1 makes3N4-Bi1-xGdxVO4The SEM figure of composite photo-catalyst, as can be seen from the figure, the g-C making3N4-Bi1-xGdxVO4Composite photo-catalyst is even spherical shape structure.
Fig. 4 is the spherical g-C that embodiment 1 makes3N4-Bi1-xGdxVO4The absorbance change curve of composite photo-catalyst rhodamine B degradation solution under ultraviolet light has degraded 89.69% in 25min, illustrates that it has good photocatalysis performance, can be used in degradation of organic substances and environmental contaminants.
Embodiment 2:
Step 1: by Bi (NO3)3·5H2O is dissolved in 20ml deionized water, under room temperature, stirs 20min to stirring on magnetic stirring apparatus, obtains Bi (NO3)3·5H2O concentration is the bismuth salting liquid of 0.4mol/L; By NH4VO3Be dissolved in the 20ml deionized water of 80 DEG C, on magnetic stirring apparatus, add thermal agitation 11min with the temperature of 40 DEG C, be transparent brown color to vanadic salts solution, obtain NH4VO3Concentration is the vanadic salts solution of 0.4mol/L, and it is long that attention can not be heated mixing time, and cause occurring yellow mercury oxide.
Step 2: prepared by step 1 mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, on magnetic stirring apparatus, stir 20min to stirring, obtain mixed liquor, then be that the NaOH solution of 4mol/L is as mineralizer to adding concentration in mixed liquor, regulating the pH value of mixed liquor is 9.4, then on magnetic stirring apparatus, stir 20min, make mixed liquor A; Notice that NaOH solution, in the time of preparation, should use the dry NaOH reagent of sheet, can not use graininess NaOH, unstable to prevent the NaOH solution alkalescence of preparation.
Step 3: by C3N4Powder is scattered in 10mL water, stirs 30min, forms suspension, C in suspension3N4Concentration be 4.6g/L; Suspension is added in mixed liquor A, stir 20min, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is 5:95; Wherein C3N4With melamine (C3H6N6) in air 550 DEG C of calcinings within 4 hours, make, after calcining, present faint yellow caking, need to be ground to fineness be below 0.088mm;
Step 4: by Gd (NO3)3·6H2O adds in mixed liquid B, stirs 20min, forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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 of 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; After question response completes, naturally cool to room temperature, take out the precipitation in reactor, respectively wash 3 times with deionized water washing and absolute ethyl alcohol, finally dry 11h in 75 DEG C of non-airtight isoperibols, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
Embodiment 3:
Step 1: by Bi (NO3)3·5H2O is dissolved in 20ml deionized water, under room temperature, stirs 25min to stirring on magnetic stirring apparatus, obtains Bi (NO3)3·5H2O concentration is the bismuth salting liquid of 0.6mol/L; By NH4VO3Be dissolved in the 20ml deionized water of 90 DEG C, on magnetic stirring apparatus, add thermal agitation 10min with the temperature of 50 DEG C, be transparent brown color to vanadic salts solution, obtain NH4VO3Concentration is the vanadic salts solution of 0.6mol/L, and it is long that attention can not be heated mixing time, and cause occurring yellow mercury oxide.
Step 2: prepared by step 1 mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, on magnetic stirring apparatus, stir 25min to stirring, obtain mixed liquor, then be that the NaOH solution of 6mol/L is as mineralizer to adding concentration in mixed liquor, regulating the pH value of mixed liquor is 9.35, then on magnetic stirring apparatus, stir 25min, make mixed liquor A; Notice that NaOH solution, in the time of preparation, should use the dry NaOH reagent of sheet, can not use graininess NaOH, unstable to prevent the NaOH solution alkalescence of preparation.
Step 3: by C3N4Powder is scattered in 10mL water, stirs 25min, forms suspension, C in suspension3N4Concentration be 55.2g/L; Suspension is added in mixed liquor A, stir 25min, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is 40:60; Wherein C3N4With melamine (C3H6N6) in air 580 DEG C of calcinings within 3.5 hours, make, after calcining, present faint yellow caking, need to be ground to fineness be below 0.088mm;
Step 4: by Gd (NO3)3·6H2O adds in mixed liquid B, stirs 25min, forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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 of 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; After question response completes, naturally cool to room temperature, take out the precipitation in reactor, respectively wash 3 times with deionized water washing and absolute ethyl alcohol, finally dry 10h in 85 DEG C of non-airtight isoperibols, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
Embodiment 4:
Step 1: by Bi (NO3)3·5H2O is dissolved in 20ml deionized water, under room temperature, stirs 22min to stirring on magnetic stirring apparatus, obtains Bi (NO3)3·5H2O concentration is the bismuth salting liquid of 0.45mol/L; By NH4VO3Be dissolved in the 20ml deionized water of 82 DEG C, on magnetic stirring apparatus, add thermal agitation 15min with the temperature of 42 DEG C, be transparent brown color to vanadic salts solution, obtain NH4VO3Concentration is the vanadic salts solution of 0.45mol/L, and it is long that attention can not be heated mixing time, and cause occurring yellow mercury oxide.
Step 2: prepared by step 1 mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, on magnetic stirring apparatus, stir 22min to stirring, obtain mixed liquor, then be that the NaOH solution of 4.5mol/L is as mineralizer to adding concentration in mixed liquor, regulating the pH value of mixed liquor is 9.32, then on magnetic stirring apparatus, stir 22min, make mixed liquor A; Notice that NaOH solution, in the time of preparation, should use the dry NaOH reagent of sheet, can not use graininess NaOH, unstable to prevent the NaOH solution alkalescence of preparation.
Step 3: by C3N4Powder is scattered in 10mL water, stirs 22min, forms suspension, C in suspension3N4Concentration be 36.8g/L; Suspension is added in mixed liquor A, stir 22min, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is 29:71; Wherein C3N4With melamine (C3H6N6) in air 550 DEG C of calcinings within 4 hours, make, after calcining, present faint yellow caking, need to be ground to fineness be below 0.088mm;
Step 4: by Gd (NO3)3·6H2O adds in mixed liquid B, stirs 22min, forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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 of 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; After question response completes, naturally cool to room temperature, take out the precipitation in reactor, respectively wash 3 times with deionized water washing and absolute ethyl alcohol, finally dry 11.5h in 78 DEG C of non-airtight isoperibols, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
Embodiment 5
Step 1: by Bi (NO3)3·5H2O is dissolved in 20ml deionized water, under room temperature, stirs 28min to stirring on magnetic stirring apparatus, obtains Bi (NO3)3·5H2O concentration is the bismuth salting liquid of 0.55mol/L; By NH4VO3Be dissolved in the 20ml deionized water of 88 DEG C, on magnetic stirring apparatus, add thermal agitation 12min with the temperature of 48 DEG C, be transparent brown color to vanadic salts solution, obtain NH4VO3Concentration is the vanadic salts solution of 0.55mol/L, and it is long that attention can not be heated mixing time, and cause occurring yellow mercury oxide.
Step 2: prepared by step 1 mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, on magnetic stirring apparatus, stir 28min to stirring, obtain mixed liquor, then be that the NaOH solution of 5.5mol/L is as mineralizer to adding concentration in mixed liquor, regulating the pH value of mixed liquor is 9.37, then on magnetic stirring apparatus, stir 28min, make mixed liquor A; Notice that NaOH solution, in the time of preparation, should use the dry NaOH reagent of sheet, can not use graininess NaOH, unstable to prevent the NaOH solution alkalescence of preparation.
Step 3: by C3N4Powder is scattered in 10mL water, stirs 28min, forms suspension, C in suspension3N4Concentration be 27.6g/L; Suspension is added in mixed liquor A, stir 28min, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is 23:77; Wherein C3N4With melamine (C3H6N6) in air 600 DEG C of calcinings within 3 hours, make, after calcining, present faint yellow caking, need to be ground to fineness be below 0.088mm;
Step 4: by Gd (NO3)3·6H2O adds in mixed liquid B, stirs 28min, forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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 of 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; After question response completes, naturally cool to room temperature, take out the precipitation in reactor, respectively wash 3 times with deionized water washing and absolute ethyl alcohol, finally dry 10.5h in 82 DEG C of non-airtight isoperibols, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
Embodiment 6
Step 1: by 0.01molBi (NO3)3·5H2O is dissolved in 20ml deionized water, under room temperature, stirs 30min to stirring on magnetic stirring apparatus, obtains Bi (NO3)3·5H2O concentration is the bismuth salting liquid of 0.5mol/L; By 0.01molNH4VO3Be dissolved in the 20ml deionized water of 85 DEG C, on magnetic stirring apparatus, add thermal agitation 14min with the temperature of 45 DEG C, be transparent brown color to vanadic salts solution, obtain NH4VO3Concentration is the vanadic salts solution of 0.5mol/L, and it is long that attention can not be heated mixing time, and cause occurring yellow mercury oxide.
Step 2: prepared by step 1 mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, on magnetic stirring apparatus, stir 30min to stirring, obtain mixed liquor, then be that the NaOH solution of 5mol/L is as mineralizer to adding concentration in mixed liquor, regulating the pH value of mixed liquor is 9.38, then on magnetic stirring apparatus, stir 30min, make mixed liquor A; Notice that NaOH solution, in the time of preparation, should use the dry NaOH reagent of sheet, can not use graininess NaOH, unstable to prevent the NaOH solution alkalescence of preparation.
Step 3: by C3N4Powder is scattered in 10mL water, stirs 20min, forms suspension, C in suspension3N4Concentration be 11.04g/L; Suspension is added in mixed liquor A, stir 30min, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2The mol ratio of O is 11:89; Wherein C3N4With melamine (C3H6N6) in air 570 DEG C of calcinings within 3.5 hours, make, after calcining, present faint yellow caking, need to be ground to fineness be below 0.088mm;
Step 4: by Gd (NO3)3·6H2O adds in mixed liquid B, stirs 30min, forms precursor liquid; Gd (NO in precursor liquid3)3·6H2O and Bi (NO3)3·5H2The 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 of 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; After question response completes, naturally cool to room temperature, take out the precipitation in reactor, respectively wash 3 times with deionized water washing and absolute ethyl alcohol, finally dry 12h in 80 DEG C of non-airtight isoperibols, obtains spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
The spherical g-C that the present invention makes3N4-Bi1-xGdxVO4Composite photo-catalyst is g-C3N4And Bi1-xGdxVO4Mixed powder, wherein g-C3N4With Bi1-xGdxVO4Mol ratio be (5～60): (95～40), Bi1-xGdxVO4For Tetragonal, space structure group is I41/admz, x=0.04～0.08, g-C3N4Be six side's phases, space structure group is P3. This composite photo-catalyst has the spherical shape pattern being assembled by single-size, and specific area is large, even particle size distribution, and ball particle diameter is along with C3N4Being on the increase of content and reducing, and particle diameter distributes more and more narrow. Spherical g-C provided by the invention3N4-Bi1-xGdxVO4Composite photo-catalyst can be good at C3N4And BiVO4Advantage carry out complementation, through photocatalysis test, prove spherical g-C provided by the invention3N4-Bi1-xGdxVO4Composite 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 any equivalence that those of ordinary skill in the art take technical solution of the present invention by reading description of the present invention, is claim of the present invention and contains.
Claims (8)
1. a spherical g-C3N4-Bi1-xGdxVO4The preparation method of composite photo-catalyst, is characterized in that,Comprise the following steps:
Step 1, by Bi (NO3)3·5H2O is soluble in water, stirs, and obtains bismuth salting liquid, by NH4VO3Be dissolved in hot water, heating is stirred to completely dissolves, and obtains vanadic salts solution; Wherein Bi (NO in bismuth salting liquid3)3·5H2OConcentration be 0.4～0.6mol/L, NH in vanadic salts solution4VO3Concentration be 0.4～0.6mol/L, vanadic salts solutionBe transparent brown color, do not contain precipitation;
Step 2, mixes bismuth salting liquid and vanadic salts solution according to mole proportioning of Bi:V=1:1, stirs,Obtain mixed liquor; In mixed liquor, add mineralizer, regulating the pH value of mixed liquor is 9.3～9.4, stirs allEven, obtain mixed liquor A;
Step 3, by C3N4Powder is scattered in water, stirs, and forms suspension; Suspension is addedIn mixed liquor A, stir, obtain mixed liquid B, C in mixed liquid B3N4With Bi (NO3)3·5H2O rubsYou are than being (5～40): (95～60); Wherein C3N4Powder be by melamine in air in 550～600 DEG C of calciningsAfter 3～4 hours, obtain through grinding, its fineness is below 0.088mm; C in suspension3N4The concentration of powderBe 4.6～55.2g/L;
Step 4, by Gd (NO3)3·6H2O adds in mixed liquid B, stirs, and forms precursor liquid; ForerunnerGd (NO in liquid3)3·6H2O and Bi (NO3)3·5H2The 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, at 190～210 DEG CLower microwave hydrothermal reaction 30～50min; After having reacted, naturally cool to room temperature, by reaction generate washing of precipitate,Dry, obtain spherical g-C3N4-Bi1-xGdxVO4Composite photo-catalyst.
2. spherical g-C according to claim 13N4-Bi1-xGdxVO4The preparation side of composite photo-catalystMethod, is characterized in that: the required time that stirs in described step 1 is 20～30min; The temperature of hot waterBe 80～90 DEG C, heating is stirred to that to dissolve the required time be completely 10～15min, and heating-up temperature is 40～50 DEG C.
3. spherical g-C according to claim 13N4-Bi1-xGdxVO4The preparation side of composite photo-catalystMethod, is characterized in that: the NaOH solution that the mineralizer in described step 2 is 4～6mol/L.
4. spherical g-C according to claim 13N4-Bi1-xGdxVO4The preparation side of composite photo-catalystMethod, is characterized in that: the required time that stirs in described step 2, step 3 and step 4 is 20～30min.
5. spherical g-C according to claim 13N4-Bi1-xGdxVO4The preparation side of composite photo-catalystMethod, is characterized in that: the packing ratio of described microwave hydrothermal reaction kettle is 50%～65%.
6. spherical g-C according to claim 13N4-Bi1-xGdxVO4The preparation side of composite photo-catalystMethod, is characterized in that: being dried as dry 10～12h at 75～85 DEG C in described step 5.
7. spherical g-C claimed in claim 13N4-Bi1-xGdxVO4Preparation method's system of composite photo-catalystThe spherical g-C obtaining3N4-Bi1-xGdxVO4Composite photo-catalyst, is characterized in that: its pattern is spherical, forg-C3N4And Bi1-xGdxVO4Mixed powder, wherein g-C3N4With Bi1-xGdxVO4Mol ratio be(5～60):(95～40)，Bi1-xGdxVO4For Tetragonal, space structure group is I41/admz, x=0.04～0.08,g-C3N4Be six side's phases, space structure group is P3.
8. spherical g-C claimed in claim 13N4-Bi1-xGdxVO4Preparation method's system of composite photo-catalystThe spherical g-C obtaining3N4-Bi1-xGdxVO4The application of composite photo-catalyst aspect degradable organic pollutant.
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