CN106881140B - A kind of carbonitride/graphene/(040) crystal face pucherite hetero-junctions and its preparation method and application - Google Patents
A kind of carbonitride/graphene/(040) crystal face pucherite hetero-junctions and its preparation method and application Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a kind of carbonitride/graphene/(040) crystal face pucherite hetero-junctions and its preparation method and application, first pass through hydro-thermal method synthesis (040) crystal face BiVO4Powder, and g-C is obtained by calcination method3N4Powder, then by hydro-thermal method by (040) crystal face BiVO4Powder with GO is compound obtains RGO/ (040) crystal face BiVO4Powder, finally by ultrasonic method by g-C3N4Powder and RGO/ (040) crystal face BiVO4The compound of powder obtains g-C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions.G-C after compound3N4, RGO and (040) crystal face BiVO4Three-phase coexistence simultaneously keeps respective growth tendency, g-C3N4, RGO and (040) crystal face BiVO4Between form hetero-junctions and mutual level-density parameter, be conducive to the separation in light induced electron and hole, make (040) crystal face BiVO4Optical response range becomes larger, and the separation rate of photo-generated carrier improves, to improve (040) crystal face BiVO4Photocatalysis performance.
Description
Technical field
The invention belongs to field of functional materials, are related to a kind of g-C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions and its preparation
Methods and applications.
Background technique
BiVO4It is a kind of photochemical catalyst with visible light activity, mainly there is monocline scheelite, cubic zircon mine, four directions
Three kinds of crystal forms of scheelite, wherein monoclinic phase BiVO4Forbidden bandwidth is about 2.4eV, and catalytic performance is best.The pucherite of monoclinic system
With excellent visible light response activity, lattice parameter are as follows: a=5.185, b=5.137, c=11.748, monoclinic system
BiVO4Conduction band mainly by V3d, O2pAnd Bi6pThree kinds of orbital hybridizations form, and this electronic structure makes photo-generated carrier be easy migration
To the surface of semiconductor, so that photochemical catalyst is easier that light-catalyzed reaction occurs under visible light；The width for increasing valence band, from
And the mobile space of photohole is increased, reduce the recombination rate of photo-generate electron-hole, to be more advantageous to photocatalytic process
Effective progress.Secondly the exposure of high activity crystal face also has a great impact to its performance, monoclinic phase BiVO4(040) crystal face
Provide polyatom BiVO4Center, it may be possible to which the origin that photocatalysis produces oxygen activity point is particularly helpful to catalyst surface high activity
The generation of oxidation activity species OH, to improve degradation rate.However, (040) crystal face BiVO4There is also photo-generate electron-holes
The problems such as low to separation rate, so as to cause the reduction of its photocatalytic activity.Therefore many scholars are by being modified to enhance it
Its visible light-responded ability, for example formation photocatalysis hetero-junctions, doping precious metal are modified, addition rare earth element is modified
The methods of and carbon is added.For example, Ji Tianhao et al. is received with titanate as presoma, using different mixed method legal systems
For the TiO changed2/BiVO4Nanocomposite, it is apparent red that ultraviolet spectra test result shows that the absorption of compound produces
It moves, shows that under visible light the photocatalytic activity of composite material is much higher than using the experiment of methylene blue as simulation degradation substrate
Pure BiVO4And TiO2Crystal.Suo Jing et al. combines hydro-thermal method and infusion process, using nonionic surfactant P123 as template
Agent is prepared for Cu modified BiVO under the conditions of 200 DEG C4- Cu composite material, as a result, it has been found that, compound morphosis is good, inhales
Obvious red shift occurs for take-up and absorption intensity increases very much.Chen Ying etc. combines hydro-thermal method-infusion process-roasting method in pure BiVO4
The area load Co element of catalyst, experimental result show that after reacting 1h, photocatalysis denitrification percent reaches 83.59%, and Co is most
Good load capacity is 4%, and reaction temperature is 400 DEG C, calcining time 1h.
RGO is a kind of two-dimentional carbon material of layer structure, and band gap is almost nil, and electric conductivity is high, large specific surface area, adsorption energy
Power is strong, can be used as good catalyst promoter, and can effectively facilitate the separative efficiency of photo-generated carrier, greatly enhancing photocatalysis
The activity and stability of material.g-C3N4Due to forbidden bandwidth about 2.7eV, chemical stability is good, preparation method is easy the advantages that by
To extensive concern.
So far, g-C3N4/ RGO/ (040) crystal face BiVO4There is not been reported for the work of the preparation method of compound,
There is no patent and document report g-C3N4/ RGO/ (040) crystal face BiVO4The preparation method of compound.
Summary of the invention
The purpose of the present invention is to provide a kind of carbonitride/graphene/(040) crystal face pucherite hetero-junctions and its preparation sides
Method and application carry out three-phase composite using ultrasonic method, and the more other chemical synthesis of process flow are simple, successfully synthesized g-
C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions improves BiVO4Photocatalysis performance.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of carbonitride/graphene/(040) crystal face pucherite hetero-junctions, comprising the following steps:
Step 1, by Bi (NO3)3·5H2O is dissolved in dilute HNO3In, it stirs to clarify, NH is then added4VO3, stirring 50~
80min forms precursor liquid A；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:1；
Step 2, by precursor liquid A at 70~90 DEG C 13~16h of hydro-thermal reaction, be made (040) crystal face BiVO4Precipitating, will
The washing of precipitate, drying obtain (040) crystal face BiVO4Powder；
Step 3, graphene oxide is dissolved in the ethanol water that volume fraction is 40~60%, ultrasonic disperse simultaneously stirs
Uniformly, dust technology is then added, ultrasonic disperse simultaneously stirs evenly, and adds NaOH solution, and ultrasonic disperse is simultaneously stirred evenly, obtained
GO solution；Wherein HNO in graphene oxide and the dust technology of addition3And in NaOH solution NaOH molar ratio be (0.35~
0.7):1:1；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and 30~60min of stirring forms forerunner
Liquid B, by precursor liquid B at 150~180 DEG C 80~120min of hydro-thermal reaction, obtain RGO/ (040) crystal face BiVO4Precipitating, by this
Washing of precipitate, drying obtain RGO/ (040) crystal face BiVO4Powder；(040) the crystal face BiVO being wherein added4Powder and GO solution
The mass ratio of middle GO is (3~5): 1；
Step 5, by CO (NH2)2530~580 DEG C are raised to from room temperature, calcines 2~4h, g-C is made3N4Powder；
Step 6, under agitation, by g-C obtained3N4Powder is dissolved in deionized water, and stirring, ultrasound are equal to mixing
It is even, obtain g-C3N4Solution；
Step 7, under agitation, by the RGO/ prepared (040) crystal face BiVO4G-C is added in powder3N4In solution, stir
30~60min is mixed, precursor liquid C is obtained, wherein RGO/ (040) the crystal face BiVO being added4Powder and g-C3N4G-C in solution3N4's
Mass ratio is (2~8): (8~2)；
Step 8, precursor liquid C is subjected to ultrasonic reaction at room temperature, will be obtained after the washing of precipitate of reaction generation, drying
Carbonitride/graphene/(040) crystal face pucherite hetero-junctions.
Bi in precursor liquid A in the step 13+Concentration be 0.1~0.3mol/L, dilute HNO3Concentration be 1~3mol/L.
Drying in the step 2, step 4 and step 8 is in 60~80 DEG C of 8~10h of freeze-day with constant temperature.
The concentration of graphene oxide is 0.01~0.02g/mL, dust technology and NaOH solution in GO solution in the step 3
Concentration be 2~4mol/L, the addition speed of dust technology and NaOH solution is 1~3 drop/sec.
It each ultrasonic disperse and is stirred evenly in the step 3, is first at 40~60 DEG C with the power of 80~100W
60~80min of ultrasonic disperse, is stirred for 10~30min.
Heating rate in the step 5 is 8~12 DEG C/min；
G-C in the step 63N4The concentration of solution is 0.01~0.03g/mL.
The ultrasonic reaction time in the step 8 is 1~2h, and ultrasonic power is 80~100W.
Carbonitride/the graphene/(040) crystal face pucherite hetero-junctions preparation method is obtained to nitrogenize carbon graphite
Alkene/(040) crystal face pucherite hetero-junctions, BiVO in the carbonitride/graphene/(040) crystal face pucherite hetero-junctions4Structure
For monoclinic phase, BiVO in carbonitride/graphene/(040) crystal face pucherite hetero-junctions4, RGO and g-C3N4Three-phase coexistence forms
Heterojunction structure, and BiVO4, RGO and g-C3N4Energy level be mutually matched.
Charge transfer resistance R after the carbonitride/graphene/(040) crystal face pucherite hetero-junctions illumination is than pure (040)
Crystal face BiVO4The R value of powder reduces 3.71 times, and carbonitride/graphene/(040) crystal face pucherite hetero-junctions shines in visible light
Under degradation rate be pure (040) crystal face BiVO46.4 times of powder.
Carbonitride/the graphene/(040) crystal face pucherite hetero-junctions is in terms of photocatalysis degradation organic contaminant
Using.
Compared with prior art, the invention has the following advantages:
Carbonitride/graphene provided by the invention/(040) crystal face pucherite hetero-junctions preparation method, first passes through hydro-thermal
Method synthesizes (040) crystal face BiVO4Powder, and g-C is obtained by calcination method3N4Powder, then by hydro-thermal method by (040) crystal face
BiVO4Powder and graphene oxide (GO) are compound, and GO is reduced into graphene (RGO) in recombination process, obtain RGO/ (040) crystal face
BiVO4Powder carries out g-C finally by ultrasonic method3N4Powder and RGO/ (040) crystal face BiVO4Powder it is compound, synthesized g-
C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions.This method ultrasonic reaction time is short, and process flow is simple.Ultrasonic method and other sides
Method, which is compared, has preparation process simple, cheap, can directly obtain the powder of well-crystallized, it is excellent to be easy to adjusting seed size size etc.
Point.Due to BiVO4And g-C3N4Band structure and crystal plane structure match very much, light induced electron can be from g-C3N4Conduction band transfer
To BiVO4Conduction band, and photohole can be from BiVO4Valence be transferred to g-C3N4Valence band, thus be conducive to light induced electron and
Efficiently separating and migrating for hole, improves the concentration of carrier；RGO excellent electric conductivity increases the concentration of carrier, effectively
Improve BiVO4The separative efficiency of photo-generated carrier, so that its photocatalysis performance be made to enhance；g-C3N4, RGO and (040) crystal face
BiVO4Hetero-junctions is formed between powder three, the formation of hetero-junctions improves the separation rate of photo-generate electron-hole pair, Neng Gouti
Height (040) crystal face BiVO4Photocatalysis performance.
In carbonitride/graphene prepared by the present invention/(040) crystal face pucherite hetero-junctions, RGO and g-C3N4Introducing simultaneously
Do not change BiVO4Object phase, be still monoclinic phase, crystal development is complete, and the exposure of (040) crystal face is good, and structural stability is good.
The good electric conductivity of RGO increases the active site of catalyst surface, effectively facilitates the migration of light induced electron, inhibits electronics-sky
Cave pair it is compound again.G-C after compound3N4, RGO and (040) crystal face BiVO4Three-phase coexistence, and three-phase syntrophism, and keep each
From growth tendency, there is between three synergistic effect.g-C3N4, RGO and (040) crystal face BiVO4Between form hetero-junctions and
Mutual level-density parameter, the formation of heterojunction structure effectively promote the multiple again of the inhibition of metastasis electron-hole pair of light induced electron
It closes, is conducive to the separation in light induced electron and hole, is conducive to the conduction of electronics, effectively facilitate the separative efficiency of photo-generated carrier,
To improve photocatalytic activity and stability, improve photoresponse intensity, optical response range becomes larger, photo-generate electron-hole pair
Separation rate increase, the separation rate of photo-generated carrier improves, to improve (040) crystal face BiVO4Photocatalysis performance.
Further, g-C produced by the present invention3N4/ RGO/ (040) crystal face BiVO4Electric charge transfer electricity after hetero-junctions illumination
Hindering R is 1.71 × 106Ω, and pure (040) crystal face BiVO4The R of powder is 6.35 × 106Ω, compound rear g-C3N4/RGO/(040)
Crystal face BiVO4Purer (040) the crystal face BiVO of the charge transfer resistance R value of hetero-junctions4Powder reduces about 3.71 times, illustrates multiple
G-C after conjunction3N4, RGO and (040) crystal face BiVO4Between the heterojunction structure that is formed effectively promoted BiVO4Photoproduction in electrode
The transmission and separation of carrier, improve the concentration of carrier.And g-C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions is can
It is light-exposed according to degradation rate after 60min up to 96% or more, and pure (040) crystal face BiVO4Powder is in visible light according to the degradation after 60min
Rate is only 15%, compound rear g-C3N4/ (040) crystal face BiVO4Purer (040) the crystal face BiVO of the degradation rate of hetero-junctions4Powder improves
About 6.4 times, greatly improve (040) crystal face BiVO4Photocatalysis performance.
Detailed description of the invention
Fig. 1 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The XRD diffracting spectrum of hetero-junctions；
Fig. 2 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The FI-IR map of hetero-junctions；
Fig. 3 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The ac impedance spectroscopy of hetero-junctions；
Fig. 4 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The photocatalytic degradation map of hetero-junctions.
Specific embodiment
The present invention is described further with currently preferred specific embodiment with reference to the accompanying drawing, raw material is analysis
It is pure.
Embodiment 1:
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 60min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.2mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 80 DEG C after hydro-thermal reaction 15h4Precipitating, the precipitating is through alcohol
After washing, washing, in 70 DEG C of freeze-day with constant temperature 9h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide (GO) for using the Hummers method of improvement to prepare is dissolved in volume fraction for 50%
In ethanol water, with the power ultrasonic disperse 60min of 100W at 50 DEG C, 10min is stirred, is then added with 1 drop/sec of speed
The HNO of 2mol/L3, with the power ultrasound 60min of 100W at 50 DEG C, 10min is stirred, then 2mol/L is added with 1 drop/sec of speed
NaOH solution stir 10min with the power ultrasound 60min of 100W at 50 DEG C, obtain GO solution；Wherein graphene oxide with plus
HNO in the dust technology entered3And the molar ratio of NaOH is 0.5:1:1 in NaOH solution, the concentration of graphene oxide in GO solution
For 0.02g/mL；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 60min forms precursor liquid B,
By precursor liquid B at 160 DEG C hydro-thermal reaction 100min, obtain RGO/ (040) crystal face BiVO4Precipitating, by reaction generate precipitating according to
It is secondary to be washed with dehydrated alcohol and deionized water, then the dry 10h at 70 DEG C, obtain RGO/ (040) crystal face BiVO4Powder；Wherein
(040) the crystal face BiVO being added4The mass ratio of GO is 4:1 in powder and GO solution；
Step 5, by CO (NH2)2550 DEG C are raised to the heating rate of 10 DEG C/min, calcines 3h, is made faint yellow and in more
Poroid g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.02g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 2:8
G-C is added3N4In solution, 60min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 1h, ultrasonic power 100W at room temperature, the precipitating that then generates reaction
It is successively washed with dehydrated alcohol and deionized water, dry 9h, obtains g-C at 70 DEG C3N4/ RGO/ (040) crystal face BiVO4It is heterogeneous
Knot.
Embodiment 2:
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1.8mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 55min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.18mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 78 DEG C after hydro-thermal reaction 13.5h4Precipitating, the precipitating is through alcohol
After washing, washing, in 72 DEG C of freeze-day with constant temperature 9h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide prepared (GO) is dissolved in the ethanol water that volume fraction is 40%, at 40 DEG C
With the power ultrasonic disperse 72min of 80W, 15min is stirred, the HNO of 3mol/L is then added with 2 drops/sec of speed3, at 40 DEG C
With the power ultrasound 72min of 80W, stir 15min, then the NaOH solution of 3mol/L be added with 2 drops/sec of speed, at 40 DEG C with
The power ultrasound 72min of 80W stirs 15min, obtains GO solution；Wherein HNO in graphene oxide and the dust technology of addition3And
The molar ratio of NaOH is 0.35:1:1 in NaOH solution, and the concentration of graphene oxide is 0.01g/mL in GO solution；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 50min forms precursor liquid B,
By precursor liquid B at 170 DEG C hydro-thermal reaction 90min, obtain RGO/ (040) crystal face BiVO4Precipitating, the precipitating that reaction is generated is successively
It is washed with dehydrated alcohol and deionized water, then the dry 9h at 72 DEG C, obtains RGO/ (040) crystal face BiVO4Powder；Wherein it is added
(040) crystal face BiVO4The mass ratio of GO is 3:1 in powder and GO solution；
Step 5, by CO (NH2)2530 DEG C are raised to the heating rate of 10.5 DEG C/min, 4h is calcined, is made faint yellow and is in
Cavernous g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.01g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 4:6
G-C is added3N4In solution, 40min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 1.2h, ultrasonic power 90W at room temperature, then will reaction generate it is heavy
Shallow lake is successively washed with dehydrated alcohol and deionized water, and dry 9h, obtains g-C at 72 DEG C3N4/ RGO/ (040) crystal face BiVO4It is different
Matter knot.
Embodiment 3:
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1.2mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 75min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.22mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 82 DEG C after hydro-thermal reaction 14.5h4Precipitating, the precipitating is through alcohol
After washing, washing, in 68 DEG C of freeze-day with constant temperature 9h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide prepared (GO) is dissolved in the ethanol water that volume fraction is 45%, at 45 DEG C
With the power ultrasonic disperse 75min of 90W, 20min is stirred, the HNO of 4mol/L is then added with 3 drops/sec of speed3, at 45 DEG C
With the power ultrasound 75min of 90W, stir 20min, then the NaOH solution of 4mol/L be added with 3 drops/sec of speed, at 45 DEG C with
The power ultrasound 75min of 90W stirs 20min, obtains GO solution；Wherein HNO in graphene oxide and the dust technology of addition3And
The molar ratio of NaOH is 0.7:1:1 in NaOH solution, and the concentration of graphene oxide is 0.014g/mL in GO solution；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 40min forms precursor liquid B,
By precursor liquid B at 180 DEG C hydro-thermal reaction 80min, obtain RGO/ (040) crystal face BiVO4Precipitating, the precipitating that reaction is generated is successively
It is washed with dehydrated alcohol and deionized water, then the dry 9h at 68 DEG C, obtains RGO/ (040) crystal face BiVO4Powder；Wherein it is added
(040) crystal face BiVO4The mass ratio of GO is 5:1 in powder and GO solution；
Step 5, by CO (NH2)2540 DEG C are raised to the heating rate of 9.5 DEG C/min, 3.5h is calcined, is made faint yellow and is in
Cavernous g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.03g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 8:2
G-C is added3N4In solution, 50min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 1.4h, ultrasonic power 95W at room temperature, then will reaction generate it is heavy
Shallow lake is successively washed with dehydrated alcohol and deionized water, and dry 9h, obtains g-C at 68 DEG C3N4/ RGO/ (040) crystal face BiVO4It is different
Matter knot.
Embodiment 4:
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1.5mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 50min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.25mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 85 DEG C after hydro-thermal reaction 14h4Precipitating, the precipitating is through alcohol
After washing, washing, in 75 DEG C of freeze-day with constant temperature 8.5h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide prepared (GO) is dissolved in the ethanol water that volume fraction is 55%, at 55 DEG C
With the power ultrasonic disperse 68min of 85W, 25min is stirred, the HNO of 2.5mol/L is then added with 1.5 drops/sec of speed3, 55
With the power ultrasound 68min of 85W at DEG C, 25min is stirred, then the NaOH solution of 2.5mol/L is added with 1.5 drops/sec of speed,
With the power ultrasound 68min of 85W at 55 DEG C, 25min is stirred, GO solution is obtained；Wherein in graphene oxide and the dust technology of addition
HNO3And the molar ratio of NaOH is 0.55:1:1 in NaOH solution, the concentration of graphene oxide is 0.015g/mL in GO solution；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 55min forms precursor liquid B,
By precursor liquid B at 150 DEG C hydro-thermal reaction 120min, obtain RGO/ (040) crystal face BiVO4Precipitating, by reaction generate precipitating according to
It is secondary to be washed with dehydrated alcohol and deionized water, then the dry 8.5h at 75 DEG C, obtain RGO/ (040) crystal face BiVO4Powder；Wherein
(040) the crystal face BiVO being added4The mass ratio of GO is 3.8:1 in powder and GO solution；
Step 5, by CO (NH2)2560 DEG C are raised to the heating rate of 8 DEG C/min, calcines 2.8h, is made faint yellow and in more
Poroid g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.018g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 3:7
G-C is added3N4In solution, 30min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 1.6h, ultrasonic power 85W at room temperature, then will reaction generate it is heavy
Shallow lake is successively washed with dehydrated alcohol and deionized water, and dry 8.5h, obtains g-C at 75 DEG C3N4/ RGO/ (040) crystal face BiVO4
Hetero-junctions.
Embodiment 5:
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 2.5mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 70min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.15mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 75 DEG C after hydro-thermal reaction 15.5h4Precipitating, the precipitating is through alcohol
After washing, washing, in 65 DEG C of freeze-day with constant temperature 9.5h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide prepared (GO) is dissolved in the ethanol water that volume fraction is 60%, at 60 DEG C
With the power ultrasonic disperse 70min of 95W, 30min is stirred, the HNO of 3.5mol/L is then added with 2.5 drops/sec of speed3, 60
With the power ultrasound 70min of 95W at DEG C, 30min is stirred, then the NaOH solution of 3.5mol/L is added with 2.5 drops/sec of speed,
With the power ultrasound 70min of 95W at 60 DEG C, 30min is stirred, GO solution is obtained；Wherein in graphene oxide and the dust technology of addition
HNO3And the molar ratio of NaOH is 0.4:1:1 in NaOH solution, the concentration of graphene oxide is 0.016g/mL in GO solution；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 45min forms precursor liquid B,
By precursor liquid B at 155 DEG C hydro-thermal reaction 110min, obtain RGO/ (040) crystal face BiVO4Precipitating, by reaction generate precipitating according to
It is secondary to be washed with dehydrated alcohol and deionized water, then the dry 9.5h at 65 DEG C, obtain RGO/ (040) crystal face BiVO4Powder；Wherein
(040) the crystal face BiVO being added4The mass ratio of GO is 3.5:1 in powder and GO solution；
Step 5, by CO (NH2)2570 DEG C are raised to the heating rate of 9 DEG C/min, calcines 2.5h, is made faint yellow and in more
Poroid g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.015g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 7:3
G-C is added3N4In solution, 35min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 1.8h, ultrasonic power 80W at room temperature, then will reaction generate it is heavy
Shallow lake is successively washed with dehydrated alcohol and deionized water, and dry 10h, obtains g-C at 60 DEG C3N4/ RGO/ (040) crystal face BiVO4It is different
Matter knot.
Embodiment 6
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 2mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 80min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.1mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 70 DEG C after hydro-thermal reaction 16h4Precipitating, the precipitating is through alcohol
After washing, washing, in 60 DEG C of freeze-day with constant temperature 10h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide prepared (GO) is dissolved in the ethanol water that volume fraction is 52%, at 52 DEG C
With the power ultrasonic disperse 65min of 100W, 12min is stirred, the HNO of 2.2mol/L is then added with 1.2 drops/sec of speed3, 52
With the power ultrasound 65min of 100W at DEG C, 12min is stirred, then the NaOH solution of 2.2mol/L is added with 1.2 drops/sec of speed,
With the power ultrasound 65min of 100W at 52 DEG C, 12min is stirred, GO solution is obtained；Wherein in graphene oxide and the dust technology of addition
HNO3And the molar ratio of NaOH is 0.6:1:1 in NaOH solution, the concentration of graphene oxide is 0.012g/mL in GO solution；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 35min forms precursor liquid B,
By precursor liquid B at 165 DEG C hydro-thermal reaction 95min, obtain RGO/ (040) crystal face BiVO4Precipitating, the precipitating that reaction is generated is successively
It is washed with dehydrated alcohol and deionized water, then the dry 10h at 60 DEG C, obtains RGO/ (040) crystal face BiVO4Powder；Wherein plus
(040) the crystal face BiVO entered4The mass ratio of GO is 4.5:1 in powder and GO solution；
Step 5, by CO (NH2)2580 DEG C are raised to the heating rate of 11 DEG C/min, calcines 2h, is made faint yellow and in more
Poroid g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.025g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 5:5
G-C is added3N4In solution, 45min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 1.5h, ultrasonic power 100W at room temperature, then will reaction generate it is heavy
Shallow lake is successively washed with dehydrated alcohol and deionized water, and dry 9.5h, obtains g-C at 65 DEG C3N4/ RGO/ (040) crystal face BiVO4
Hetero-junctions.
Embodiment 7
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 3mol/L's under agitation with uniform slowly speed
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution clarification4VO3, 65min is stirred, precursor liquid A is formed, it is preceding
Drive Bi in liquid A3+Concentration be 0.3mol/L；
Step 2, (040) crystal face BiVO is made in precursor liquid A at 90 DEG C after hydro-thermal reaction 13h4Precipitating, the precipitating is through alcohol
After washing, washing, in 80 DEG C of freeze-day with constant temperature 8h, (040) crystal face BiVO is obtained4Powder；
Step 3, the graphene oxide prepared (GO) is dissolved in the ethanol water that volume fraction is 48%, at 48 DEG C
With the power ultrasonic disperse 80min of 90W, 18min is stirred, the HNO of 2.8mol/L is then added with 1.8 drops/sec of speed3, 48
With the power ultrasound 80min of 90W at DEG C, 18min is stirred, then the NaOH solution of 2.8mol/L is added with 1.8 drops/sec of speed,
With the power ultrasound 80min of 90W at 48 DEG C, 18min is stirred, GO solution is obtained；Wherein in graphene oxide and the dust technology of addition
HNO3And the molar ratio of NaOH is 0.45:1:1 in NaOH solution, the concentration of graphene oxide is 0.018g/mL in GO solution；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and stirring 30min forms precursor liquid B,
By precursor liquid B at 175 DEG C hydro-thermal reaction 85min, obtain RGO/ (040) crystal face BiVO4Precipitating, the precipitating that reaction is generated is successively
It is washed with dehydrated alcohol and deionized water, then the dry 8h at 80 DEG C, obtains RGO/ (040) crystal face BiVO4Powder；Wherein it is added
(040) crystal face BiVO4The mass ratio of GO is 4.2:1 in powder and GO solution；
Step 5, by CO (NH2)2555 DEG C are raised to the heating rate of 12 DEG C/min, 3.2h is calcined, is made faint yellow and is in
Cavernous g-C3N4Powder；
Step 6, under agitation by g-C obtained3N4Powder is dissolved in deionized water, stirring, ultrasonic disperse to g-
C3N4Solution colour is thin out, until uniform, obtains the g-C that concentration is 0.022g/mL3N4Solution；
Step 7, under magnetic stirring, by the RGO/ prepared (040) crystal face BiVO4Powder is slow with the mass ratio of 6:4
G-C is added3N4In solution, 55min is stirred, precursor liquid C is obtained；
Step 8, by precursor liquid C ultrasonic disperse 2h, ultrasonic power 90W at room temperature, the precipitating that then generates reaction
It is successively washed with dehydrated alcohol and deionized water, dry 8h, obtains g-C at 80 DEG C3N4/ RGO/ (040) crystal face BiVO4It is heterogeneous
Knot.
Fig. 1 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The XRD diagram of hetero-junctions, it can be seen that RGO
And g-C3N4Introducing do not change BiVO4Object phase, BiVO4It is still monoclinic phase.
Fig. 2 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The FT-IR of hetero-junctions schemes, it can be seen that
GO is originally in 1050,1220,1620,1730cm-1The absorption peak at place disappears, still reservation 1540cm-1And 3450cm-1Place absorbs
Peak, this illustrates that GO has been reduced to RGO, to know to be successfully prepared out g-C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions.
Fig. 3 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The AC impedance figure of hetero-junctions, in EIS
The radius size of Nyquist curve reflects the size of electrode surface reaction rate and the size of electrode resistance.Radius is bigger
Illustrate that electrode surface reaction rate is smaller, charge transfer resistance is bigger.It can be seen that g-C3N4/ RGO/ (040) crystal face BiVO4
Hetero-junctions and (040) crystal face BiVO4Significant change, illumination occurs before and after each Nyquist null circle arc radius illumination of powder
Radius of curvature afterwards is significantly less than the sample of subdued light conditions.Wherein charge transfer resistance (R) is main research object, from table 1
Known to RGO/ (040) crystal face BiVO after illumination4R be 3.43 × 106Ω, (040) crystal face BiVO4The R of powder is 6.35 × 106
Ω, R value reduce about 2 times, g-C3N4/ RGO/ (040) crystal face BiVO4The R of hetero-junctions is 1.71 × 106Ω, than (040) crystal face
BiVO4The R value of powder reduces about 3.71 times, shows g-C3N4, RGO and (040) crystal face BiVO4Between the heterogeneous junction that is formed
Structure has effectively promoted BiVO4The transmission and separation of photo-generated carrier, improve the concentration of carrier in electrode.
The g-C prepared by the present invention of table 13N4/ RGO/ (040) crystal face BiVO4The ZsimpWin fitting data of hetero-junctions
Fig. 4 is g-C prepared by the present invention3N4/ RGO/ (040) crystal face BiVO4The degradation map of hetero-junctions rhodamine B degradation,
It can be seen that g-C3N4/ RGO/ (040) crystal face BiVO4Hetero-junctions in visible light according to degradation rate after 60min up to 96% or more,
RGO/ (040) crystal face BiVO4The degradation rate of powder is only 15%, pure (040) crystal face BiVO4The degradation rate of powder is only 15%, g-
C3N4/ RGO/ (040) crystal face BiVO4Degradation rate ratio RGO/ (040) crystal face BiVO of hetero-junctions4Powder and pure (040) crystal face BiVO4
The degradation rate of powder improves 6.4 times, greatly improves (040) crystal face BiVO4Photocatalysis performance.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent transformation taken, all are covered by the claims of the invention.
Claims (10)
1. a kind of carbonitride/graphene/(040) crystal face pucherite hetero-junctions preparation method, which is characterized in that including following step
It is rapid:
Step 1, by Bi (NO3)3·5H2O is dissolved in dilute HNO3In, it stirs to clarify, NH is then added4VO3, 50~80min is stirred,
Form precursor liquid A；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:1；
Step 2, by precursor liquid A at 70~90 DEG C 13~16h of hydro-thermal reaction, be made (040) crystal face BiVO4Precipitating, by the precipitating
Washing, drying, obtain (040) crystal face BiVO4Powder；
Step 3, graphene oxide is dissolved in the ethanol water that volume fraction is 40~60%, ultrasonic disperse simultaneously stirs equal
It is even, dust technology is then added, ultrasonic disperse simultaneously stirs evenly, and adds NaOH solution, and ultrasonic disperse simultaneously stirs evenly, and obtains GO
Solution；Wherein HNO in graphene oxide and the dust technology of addition3And in NaOH solution NaOH molar ratio be (0.35~
0.7):1:1；
Step 4, (040) the crystal face BiVO that will be prepared4Powder is added in GO solution, and 30~60min of stirring forms precursor liquid B, will
Precursor liquid B 80~120min of hydro-thermal reaction at 150~180 DEG C obtains RGO/ (040) crystal face BiVO4Precipitating, which is washed
It washs, dry, obtain RGO/ (040) crystal face BiVO4Powder；(040) the crystal face BiVO being wherein added4GO in powder and GO solution
Mass ratio is (3~5): 1；
Step 5, by CO (NH2)2530~580 DEG C are raised to from room temperature, calcines 2~4h, g-C is made3N4Powder；
Step 6, under agitation, by g-C obtained3N4Powder is dissolved in deionized water, and stirring, ultrasound are obtained to being uniformly mixed
To g-C3N4Solution；
Step 7, under agitation, by the RGO/ prepared (040) crystal face BiVO4G-C is added in powder3N4In solution, stirring 30
~60min obtains precursor liquid C, wherein RGO/ (040) the crystal face BiVO being added4Powder and g-C3N4G-C in solution3N4Quality
Than for (2~8): (8~2)；
Step 8, precursor liquid C is subjected to ultrasonic reaction at room temperature, will be nitrogenized after the washing of precipitate of reaction generation, drying
Carbon graphite alkene/(040) crystal face pucherite hetero-junctions.
2. carbonitride/graphene according to claim 1/(040) crystal face pucherite hetero-junctions preparation method, feature
It is, Bi in precursor liquid A in the step 13+Concentration be 0.1~0.3mol/L, dilute HNO3Concentration be 1~3mol/L.
3. carbonitride/graphene according to claim 1/(040) crystal face pucherite hetero-junctions preparation method, feature
It is, the drying in the step 2, step 4 and step 8 is in 60~80 DEG C of 8~10h of freeze-day with constant temperature.
4. carbonitride/graphene according to claim 1/(040) crystal face pucherite hetero-junctions preparation method, feature
Be, the concentration of graphene oxide is 0.01~0.02g/mL in GO solution in the step 3, dust technology and NaOH solution it is dense
Spending is 2~4mol/L, and the addition speed of dust technology and NaOH solution is 1~3 drop/sec.
5. carbonitride/graphene according to claim 1/(040) crystal face pucherite hetero-junctions preparation method, feature
It is, each ultrasonic disperse and is stirred evenly in the step 3, is first at 40~60 DEG C with the power ultrasound of 80~100W
Disperse 60~80min, is stirred for 10~30min.
6. carbonitride/graphene according to claim 1/(040) crystal face pucherite hetero-junctions preparation method, feature
It is, the heating rate in the step 5 is 8~12 DEG C/min；G-C in the step 63N4The concentration of solution be 0.01~
0.03g/mL。
7. carbonitride/graphene according to claim 1/(040) crystal face pucherite hetero-junctions preparation method, feature
It is, the ultrasonic reaction time in the step 8 is 1~2h, and ultrasonic power is 80~100W.
8. carbonitride/graphene described in any one of claim 1-7/(040) crystal face pucherite hetero-junctions preparation side
Carbonitride/graphene made from method/(040) crystal face pucherite hetero-junctions, which is characterized in that the carbonitride/graphene/
(040) BiVO in crystal face pucherite hetero-junctions4Structure be monoclinic phase, carbonitride/graphene/(040) crystal face pucherite is heterogeneous
BiVO in knot4, RGO and g-C3N4Three-phase coexistence forms heterojunction structure, and BiVO4, RGO and g-C3N4Energy level mutual
Match.
9. carbonitride/graphene according to claim 8/(040) crystal face pucherite hetero-junctions, it is characterised in that: described
Charge transfer resistance R after carbonitride/graphene/(040) crystal face pucherite hetero-junctions illumination is than pure (040) crystal face BiVO4Powder
The R value of body reduces 3.71 times, and degradation rate of carbonitride/graphene/(040) the crystal face pucherite hetero-junctions under visible light photograph is
Pure (040) crystal face BiVO46.4 times of powder.
10. carbonitride/graphene described in claim 8 or 9/(040) crystal face pucherite hetero-junctions is organic in photocatalytic degradation
Application in terms of pollutant.
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| CN108855077A (en) * | 2018-05-30 | 2018-11-23 | 陕西科技大学 | Ag-BiVO4Crystal face/MnOxCrystal face BiVO4Photochemical catalyst and preparation method thereof |
| CN110327965A (en) * | 2019-08-14 | 2019-10-15 | 齐鲁工业大学 | A kind of two dimension pucherite/graphene/carbonitride composite material and preparation method and application |
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| CN112973757B (en) * | 2021-03-08 | 2022-11-08 | 合肥工业大学 | Bismuth vanadate quantum dot/RGO/graphite phase carbon nitride ternary composite photocatalyst and preparation method thereof |
| CN112973756A (en) * | 2021-03-08 | 2021-06-18 | 合肥工业大学 | Rod-shaped bismuth vanadate/RGO/graphite phase carbon nitride photocatalytic material and preparation method thereof |
| CN115069292A (en) * | 2022-08-08 | 2022-09-20 | 中交七鲤古镇(赣州)文化旅游有限公司 | Preparation method and application of graphite carbon nitride/nitrogen-doped graphene/bismuth vanadate Z-type photocatalyst |
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