CN107051567A - A kind of carbonitride/(040) crystal face pucherite hetero-junctions and its preparation method and application - Google Patents
A kind of carbonitride/(040) crystal face pucherite hetero-junctions and its preparation method and application Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000002845 discoloration Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 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
- 229940043267 rhodamine b Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical group [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of carbonitride/(040) crystal face pucherite hetero-junctions and its preparation method and application, this method first passes through hydro-thermal method synthesis (040) crystal face BiVO4Powder, and g C are obtained by calcination method3N4Powder, then by (040) the crystal face BiVO prepared4Powder is dissolved in ultrasonic uniform g C3N4Agitated to obtain precursor liquid in the aqueous solution, precursor liquid carries out ultrasonic reaction at normal temperatures, and g C are made3N4/ (040) crystal face BiVO4Heterojunction photocatalyst, g C after being combined3N4With (040) crystal face BiVO4Two-phase coexistent, and two-phase syntrophism, and keep respective growth tendency, g C3N4(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 BiVO4Photoresponse scope becomes big, and the separation rate of photo-generated carrier is improved, so as to improve (040) crystal face BiVO4Photocatalysis performance under visible light.
Description
Technical field
The invention belongs to field of functional materials, it is related to a kind of g-C3N4/ (040) crystal face BiVO4Hetero-junctions and preparation method thereof
And application.
Background technology
BiVO4Mainly there are three kinds of crystal structures, be respectively cubic scheelite-type structure, monocline scheelite-type structure and cubic zircon
Structure.Tetragonal is main to have an absorption band in ultraviolet region, and the BiVO of monoclinic phase4In addition to ultraviolet region absorption band, visible
Also there is obvious absorption band in light area.The BiVO of monoclinic phase4The absorption of ultraviolet region is mainly by means of electronics from O2p track transition
Formed by V3d tracks, and monoclinic phase BiVO4The absorption band of visible region then mainly by electronics from Bi6s tracks or
Bi6s and O2p hybridized orbit transits to V3d tracks and produced.Monoclinic phase pucherite energy gap is about 2.4eV, is connect very much
Solar spectrum center is bordering on, it, which absorbs threshold value, can extend to 5203nm or so.Monoclinic phase BiVO4Belong to 12/a type space groups, its
Specifically cell parameter is：A=5.195, b=11.701, c=5.092, α=90.0 °, β=90.38 °, γ=90.0 °.Monocline
Phase BiVO4In each bonding between V atoms and 4 O atoms constitute and be mutually not in contact with each other between V-O, V-O tetrahedrons, each Bi is former
Bonding composition Bi-O is octahedra between son and 6 atoms, and the coordination polyhedrom can be considered as by the four sides of two identical sizes
Body phase mutually through, and Bi-O it is octahedra between with the adjacent alternating in side, around eight V-O four sides around a Bi atom
Body, they share an O atom.
BiVO4It is a kind of novel semiconductor material, due to having the advantages that energy gap is narrow, visible light catalysis activity is high extensive
Applied to photocatalysis field.But BiVO4There is small specific surface area, low light quantum utilization rate, electronics and hole-recombination in catalyst
The problems such as probability is high, absorption property is poor, photo-generated carrier is difficult to migration, researcher proposes that BiVO can be improved by two aspects4's
Photocatalysis performance, one is to improve BiVO4The activity of itself, such as improves crystallinity, improves pattern, increases the exposure of high activity crystal face
Deng.Wherein (040) crystal face of monoclinic phase pucherite provides polyatom BiVO4Center, it may be possible to photocatalysis production oxygen activity point
Origin is particularly helpful to catalyst surface oxide of high activity active specy OH generation, improves degradation rate；Two be to BiVO4Enter
Row is modified such as：Metal deposit, nonmetal doping, surface modification, with organic matter hydridization, semiconductors coupling etc.；Wherein, by partly leading
Bluk recombination, which forms effective hetero-junctions, can improve the separation rate of photo-generated carrier, strengthen its activity.
C3N4With α, β, cube, accurate cube with five kinds of structures of class graphite-phase, wherein with g-C3N4It is most stable.In g-C3N4
In, C, N atom are all sp2Hydridization has simultaneously been connected to form the structure with similar phenyl ring hexagon, g-C by σ keys3N4With layer
Shape structure, but its interlamellar spacing is about the interlamellar spacing that 0.326nm is slightly less than graphite.Basic composition construction unit on its layer can be by
C3N3Or C6N7Constitute.g-C3N4Conduction band be by C atoms pzTrack is constituted, and its conduction band positions is about -1.30eV；And valence band
It is then by the p of N atomsZTrack is constituted, and valence band location is about 1.40eV, g-C3N4Band gap width between valency conduction band is 2.70eV.
So far, g-C is prepared using ultrasonic method3N4/ (040) crystal face BiVO4The method work of compound not yet appears in the newspapers
Road, also no patent and document report cross g-C3N4/ (040) crystal face BiVO4The method of compound.
The content of the invention
It is an object of the invention to provide a kind of carbonitride/(040) crystal face pucherite hetero-junctions and preparation method thereof and should
With being combined using ultrasonic method, the more other chemical synthesis of technological process are simple, successfully synthesized g-C3N4/ (040) is brilliant
Face BiVO4Hetero-junctions, makes (040) crystal face BiVO4Photocatalysis performance enhancing under visible light.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of carbonitride/(040) crystal face pucherite hetero-junctions, comprises the following steps：
Step 1, by Bi (NO3)3·5H2O is dissolved in dilute HNO3In, stir to clarify, then add NH4VO3, stirring 50~
80min, forms precursor liquid A；Wherein Bi (NO3)3·5H2O and NH4VO3Mol 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 BiVO4Precipitation, will
The washing of precipitate, drying, obtain (040) crystal face BiVO4Powder；
Step 3, by CO (NH2)2530~580 DEG C are raised to from room temperature, 2~4h is calcined, g-C is made3N4Powder；
Step 4, under agitation, by obtained g-C3N4Powder is dissolved in deionized water, and stirring, ultrasound are equal to mixing
It is even, obtain g-C3N4Solution；
Step 5, under agitation, by (040) the crystal face BiVO prepared4Powder adds g-C3N4In solution, stirring is equal
It is even, precursor liquid B is obtained, wherein (040) the crystal face BiVO added4Powder and g-C3N4G-C in solution3N4Mass ratio for (2~
8):(8~2)；
Step 6, precursor liquid B is subjected to ultrasonic reaction at room temperature, obtained after the washing of precipitate generated, drying will be reacted
Carbonitride/(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 and step 6 is in 60~80 DEG C of 8~10h of freeze-day with constant temperature.
Heating rate in the step 3 is 8~12 DEG C/min.
G-C in the step 43N4The concentration of solution is 0.01~0.03g/mL.
Time needed for being stirred in the step 5 is 30~60min.
The ultrasonic reaction time in the step 6 is 1~2h, and ultrasonic power is 80~100W.
Carbonitride/(040) crystal face vanadium made from the preparation method of described carbonitride/(040) crystal face pucherite hetero-junctions
BiVO in sour bismuth hetero-junctions, the carbonitride/(040) crystal face pucherite hetero-junctions4Structure be monoclinic phase, space structure group be
I2/a, BiVO4(040) crystal face it is exposed and surface is smooth, BiVO in carbonitride/(040) crystal face pucherite hetero-junctions4With g-
C3N4Two-phase coexistent, forms heterojunction structure, and BiVO4With g-C3N4Energy level be mutually matched.
Charge transfer resistance R after the carbonitride/(040) crystal face pucherite hetero-junctions illumination is than pure (040) crystal face
BiVO4The R values of powder reduce 2.98 times, and degradation rate of carbonitride/(040) the crystal face pucherite hetero-junctions under visible ray photograph is
Pure (040) crystal face BiVO46.13 times of powder.
Described carbonitride/application of (040) crystal face pucherite hetero-junctions in terms of photocatalysis degradation organic contaminant.
Compared with prior art, the invention has the advantages that：
The preparation method of the carbonitride that the present invention is provided/(040) crystal face pucherite hetero-junctions, first passes through hydro-thermal method synthesis
(040) crystal face BiVO4Powder, and g-C is obtained by calcination method3N4Powder, then g-C is carried out by ultrasonic method3N4Powder and (040)
Crystal face BiVO4Being combined for powder, has synthesized g-C3N4/ (040) crystal face BiVO4Hetero-junctions.Ultrasonic method has compared with other methods
Preparation technology is simple, cheap, can directly obtain the powder of well-crystallized, it is easy to the advantages of adjusting seed size size.Due to
BiVO4And g-C3N4Band structure and crystal plane structure match very much, light induced electron can be from g-C3N4Conduction band be transferred to BiVO4
Conduction band, and photohole can be from BiVO4Valency be transferred to g-C3N4Valence band, thus be conducive to light induced electron and hole
Efficiently separate and migrate, improve the concentration of carrier, so that both, which are combined, can improve (040) crystal face BiVO4Photocatalysis
Performance.
In carbonitride prepared by the present invention/(040) crystal face pucherite hetero-junctions, the BiVO after ULTRASONIC COMPLEX4Structure simultaneously
Do not change, be still monoclinic phase, its space structure group is I2/a, and the exposure of its (040) crystal face is good, g-C after being combined3N4With (040)
Crystal face BiVO4Two-phase coexistent, and two-phase syntrophism, and respective growth tendency is kept, develop more complete, its structural stability
Enhancing, therebetween with synergy.g-C3N4(040) crystal face BiVO4Between form hetero-junctions and mutual energy level
Match somebody with somebody, be conducive to the separation in light induced electron and hole, be conducive to the conduction of electronics, make (040) crystal face BiVO4Photoresponse scope becomes
Greatly, the separation rate of photo-generated carrier is improved, so as to improve (040) crystal face BiVO4Photocatalysis performance under visible light.
Further, g-C produced by the present invention3N4/ (040) crystal face BiVO4Charge transfer resistance R after hetero-junctions illumination
For 2.13 × 106Ω, and pure (040) crystal face BiVO4The R of powder is 6.35 × 106Ω, g-C after being combined3N4/ (040) crystal face
BiVO4Purer (040) the crystal face BiVO of charge transfer resistance R values of hetero-junctions4Powder reduces about 3 times, illustrate it is compound after photoproduction
Electronics can be from g-C3N4Conduction band be transferred to BiVO4Conduction band, be conducive to the separation and migration in light induced electron and hole, improve
The concentration of carrier.And g-C3N4/ (040) crystal face BiVO4Hetero-junctions degradation rate after visible ray shines 120min reaches
94.07%, and pure (040) crystal face BiVO4Powder is only 15.34% according to the degradation rate after 120min in visible ray, g- after being combined
C3N4/ (040) crystal face BiVO4Purer (040) the crystal face BiVO of degradation rate of hetero-junctions4Powder improves about 6.1 times, greatly carries
High (040) crystal face BiVO4Photocatalysis performance.
Brief description of the drawings
Fig. 1 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The XRD diffracting spectrums of hetero-junctions；
Fig. 2 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The SEM figures of hetero-junctions, (b) and (c) is respectively (a)
Enlarged drawing；
Fig. 3 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The AC impedance figure of hetero-junctions；
Fig. 4 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The photocatalytic degradation figure of hetero-junctions.
Embodiment
The present invention is described further with currently preferred specific embodiment below in conjunction with the accompanying drawings, raw material is analysis
It is pure.
Embodiment 1：
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 15h4Precipitation, the precipitation 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, by CO (NH2)2550 DEG C are raised to 10 DEG C/min heating rate, 3h is calcined, g-C is made3N4Powder；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.02g/mL3N4Solution；
Step 5, under magnetic stirring, with 2:8 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 60min after stirring 30min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 1h at normal temperatures, ultrasonic power is 100W, then by the precipitation of generation successively
Washed with absolute ethyl alcohol and deionized water, in 70 DEG C of dry 8h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Embodiment 2：
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1.8mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 13.5h4Precipitation, the precipitation 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, by CO (NH2)2530 DEG C are raised to 10.5 DEG C/min heating rate, 4h is calcined, g-C is made3N4Powder；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.025g/mL3N4Solution；
Step 5, under magnetic stirring, with 4:6 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 60min after stirring 40min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 1.2h at normal temperatures, ultrasonic power is 90W, then by the precipitation of generation according to
It is secondary to be washed with absolute ethyl alcohol and deionized water, in 72 DEG C of dry 9h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Embodiment 3：
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1.2mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 14.5h4Precipitation, the precipitation 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, by CO (NH2)2540 DEG C are raised to 9.5 DEG C/min heating rate, 3.5h is calcined, g-C is made3N4Powder
Body；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.015g/mL3N4Solution；
Step 5, under magnetic stirring, with 6:4 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 50min after stirring 30min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 1.4h at normal temperatures, ultrasonic power is 95W, then by the precipitation of generation according to
It is secondary to be washed with absolute ethyl alcohol and deionized water, in 68 DEG C of dry 9h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Embodiment 4：
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 1.5mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 14h4Precipitation, the precipitation 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, by CO (NH2)2560 DEG C are raised to 8 DEG C/min heating rate, 2.8h is calcined, g-C is made3N4Powder；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.01g/mL3N4Solution；
Step 5, under magnetic stirring, with 5:5 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 60min after stirring 60min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 1.6h at normal temperatures, ultrasonic power is 85W, then by the precipitation of generation according to
It is secondary to be washed with absolute ethyl alcohol and deionized water, in 75 DEG C of dry 8.5h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Embodiment 5：
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 2.5mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 15.5h4Precipitation, the precipitation 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, by CO (NH2)2570 DEG C are raised to 9 DEG C/min heating rate, 2.5h is calcined, g-C is made3N4Powder；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.03g/mL3N4Solution；
Step 5, under magnetic stirring, with 8:2 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 60min after stirring 35min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 1.8h at normal temperatures, ultrasonic power is 80W, then by the precipitation of generation according to
It is secondary to be washed with absolute ethyl alcohol and deionized water, in 65 DEG C of dry 9.5h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Embodiment 6
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 2mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 16h4Precipitation, the precipitation 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, by CO (NH2)2580 DEG C are raised to 11 DEG C/min heating rate, 2h is calcined, g-C is made3N4Powder；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.022g/mL3N4Solution；
Step 5, under magnetic stirring, with 3:7 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 60min after stirring 45min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 1.5h at normal temperatures, ultrasonic power is 100W, then by the precipitation of generation according to
It is secondary to be washed with absolute ethyl alcohol and deionized water, in 60 DEG C of dry 10h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Embodiment 7
Step 1, by 6mmoL Bi (NO3)3·5H2O is dissolved in 3mol/L's with uniform slow speed under agitation
HNO3In solution, stirring 30min is slowly added to 6mmoL NH after solution is clarified4VO3, 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 13h4Precipitation, the precipitation 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, by CO (NH2)2555 DEG C are raised to 12 DEG C/min heating rate, 3.2h is calcined, g-C is made3N4Powder；
Step 4, under agitation by obtained g-C3N4Powder is dissolved in deionized water, stirring to g-C3N4Solution face
Discoloration is light, it is uniform untill, obtain the g-C that concentration is 0.018g/mL3N4Solution；
Step 5, under magnetic stirring, with 7:3 mass ratio is by (040) the crystal face BiVO prepared4Powder is slowly added to
g-C3N4In solution, ultrasound 60min after stirring 55min obtains precursor liquid B；
Step 6, by precursor liquid B ultrasonic reaction 2h at normal temperatures, ultrasonic power is 90W, then by the precipitation of generation successively
Washed with absolute ethyl alcohol and deionized water, in 80 DEG C of dry 8h, obtain g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Fig. 1 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The XRD diffracting spectrums of hetero-junctions, g-C3N4Introducing
Do not change BiVO4Thing phase, BiVO4It is still monoclinic phase, g-C is occurred in that in 2 θ=27 ° or so3N4Characteristic diffraction peak, say
It is bright to be successfully prepared out g-C3N4/ (040) crystal face BiVO4Hetero-junctions.
Fig. 2 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The SEM figures of hetero-junctions, made (040) crystal face
BiVO4A certain degree of reunion, g-C occur for little particle3N4Exist in the form of lamella accordion, two-phase is common after ULTRASONIC COMPLEX
Growth, maintains respective growth tendency, so both ensure that the performance of respective performance again, again can be by connecing each other
Touch, strengthened synergy, be formed with the mechanism conducted beneficial to electronics.
Fig. 3 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4Nyquist in the AC impedance figure of hetero-junctions, EIS
The radius size of curve reflects the size of electrode surface reaction rate and the size of electrode resistance.The about big explanation electrode of radius
Surface reaction rate is smaller, and charge transfer resistance is bigger.As can be seen from Figure 3, g-C3N4/ (040) crystal face BiVO4Hetero-junctions and pure
(040) crystal face BiVO4Occurs significant change before and after each Nyquist null circles arc radius illumination of powder, the curvature after illumination
Radius is significantly less than the sample of subdued light conditions.Wherein charge transfer resistance (R) is main research object, as known from Table 1 g-
C3N4/ (040) crystal face BiVO4R after hetero-junctions illumination is 2.13 × 106Ω, and pure (040) crystal face BiVO4The R of powder is 6.35
×106Ω, compound rear R values reduce about 2.98 times, illustrate g-C3N4(040) crystal face BiVO4Between the heterojunction structure that is formed
It has been effectively promoted BiVO4The transmission and separation of photo-generated carrier, improve the concentration of carrier in electrode.
G-C prepared by the present invention of table 13N4/ (040) crystal face BiVO4The ZsimpWin fitting data of hetero-junctions
Fig. 4 is g-C prepared by the present invention3N4/ (040) crystal face BiVO4The degraded of the photocatalytic degradation rhodamine B of hetero-junctions
Curve map, it can be seen that g-C3N4/ (040) crystal face BiVO4Hetero-junctions degradation rate after visible ray shines 120min reaches
More than 94.07%, and pure (040) crystal face BiVO4Powder degradation rate is only 15.34%, the g-C after being combined3N4/ (040) crystal face
BiVO4Hetero-junctions is than pure (040) crystal face BiVO4The degradation rate of powder improves about 6.13 times, greatly improves (040) crystal face
BiVO4Photocatalysis performance.
Above said content is to combine specific preferred embodiment further description made for the present invention, 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 conversion taken, is that claim of the invention is covered.
Claims (10)
1. the preparation method of a kind of carbonitride/(040) crystal face pucherite hetero-junctions, it is characterised in that comprise the following steps：
Step 1, by Bi (NO3)3·5H2O is dissolved in dilute HNO3In, stir to clarify, then add NH4VO3, 50~80min is stirred,
Form precursor liquid A；Wherein Bi (NO3)3·5H2O and NH4VO3Mol 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 BiVO4Precipitation, this is precipitated
Wash, dry, obtain (040) crystal face BiVO4Powder；
Step 3, by CO (NH2)2530~580 DEG C are raised to from room temperature, 2~4h is calcined, g-C is made3N4Powder；
Step 4, under agitation, by obtained g-C3N4Powder is dissolved in deionized water, and stirring, ultrasound are obtained to well mixed
To g-C3N4Solution；
Step 5, under agitation, by (040) the crystal face BiVO prepared4Powder adds g-C3N4In solution, stir,
Precursor liquid B is obtained, wherein (040) the crystal face BiVO added4Powder and g-C3N4G-C in solution3N4Mass ratio be (2~8):(8
~2)；
Step 6, precursor liquid B is subjected to ultrasonic reaction at room temperature, nitrogenized after the washing of precipitate generated, drying will be reacted
Carbon/(040) crystal face pucherite hetero-junctions.
2. the preparation method of carbonitride according to claim 1/(040) crystal face pucherite hetero-junctions, it is characterised in that institute
State in step 1 Bi in precursor liquid A3+Concentration be 0.1~0.3mol/L, dilute HNO3Concentration be 1~3mol/L.
3. the preparation method of carbonitride according to claim 1/(040) crystal face pucherite hetero-junctions, it is characterised in that institute
It is in 60~80 DEG C of 8~10h of freeze-day with constant temperature to state the drying in step 2 and step 6.
4. the preparation method of carbonitride according to claim 1/(040) crystal face pucherite hetero-junctions, it is characterised in that institute
It is 8~12 DEG C/min to state the heating rate in step 3.
5. the preparation method of carbonitride according to claim 1/(040) crystal face pucherite hetero-junctions, it is characterised in that institute
State g-C in step 43N4The concentration of solution is 0.01~0.03g/mL.
6. the preparation method of carbonitride according to claim 1/(040) crystal face pucherite hetero-junctions, it is characterised in that institute
It is 30~60min to state the time needed for being stirred in step 5.
7. the preparation method of carbonitride according to claim 1/(040) crystal face pucherite hetero-junctions, it is characterised in that institute
It is 1~2h to state the ultrasonic reaction time in step 6, and ultrasonic power is 80~100W.
8. made from the preparation method of carbonitride/(040) crystal face pucherite hetero-junctions in claim 1-7 described in any one
Carbonitride/(040) crystal face pucherite hetero-junctions, it is characterised in that in the carbonitride/(040) crystal face pucherite hetero-junctions
BiVO4Structure be monoclinic phase, space structure group be I2/a, BiVO4(040) crystal face it is exposed and surface is smooth, carbonitride/
(040) BiVO in crystal face pucherite hetero-junctions4With g-C3N4Two-phase coexistent, forms heterojunction structure, and BiVO4With g-C3N4's
Energy level is mutually matched.
9. carbonitride according to claim 8/(040) crystal face pucherite hetero-junctions, it is characterised in that：The carbonitride/
(040) the charge transfer resistance R after the illumination of crystal face pucherite hetero-junctions is than pure (040) crystal face BiVO4The R values of powder are reduced
2.98 times, degradation rate of carbonitride/(040) the crystal face pucherite hetero-junctions under visible ray photograph is pure (040) crystal face BiVO4Powder
6.13 times.
10. carbonitride/(040) crystal face pucherite hetero-junctions described in claim 8 or 9 is in photocatalysis degradation organic contaminant side
The application in face.
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| CN109985657A (en) * | 2019-04-30 | 2019-07-09 | 燕山大学 | BiVO4/2D g-C3N4The preparation method of Z-type heterojunction photocatalyst |
| CN110102327A (en) * | 2019-04-22 | 2019-08-09 | 中南林业科技大学 | A kind of defect carbonitride coupling pucherite catalysis material and preparation method thereof and purposes |
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| CN110102327A (en) * | 2019-04-22 | 2019-08-09 | 中南林业科技大学 | A kind of defect carbonitride coupling pucherite catalysis material and preparation method thereof and purposes |
| CN109985657A (en) * | 2019-04-30 | 2019-07-09 | 燕山大学 | BiVO4/2D g-C3N4The preparation method of Z-type heterojunction photocatalyst |
| CN109985657B (en) * | 2019-04-30 | 2020-06-12 | 燕山大学 | BiVO4/2D g-C3N4Preparation method of Z-type heterojunction photocatalyst |
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| CN113896243A (en) * | 2021-09-29 | 2022-01-07 | 陕西科技大学 | BiVO4Nanosheet and preparation method and application thereof |
| CN113896243B (en) * | 2021-09-29 | 2023-08-18 | 陕西科技大学 | BiVO (binary organic acid) 4 Nanosheets, preparation method and application thereof |
| CN114100655A (en) * | 2021-10-27 | 2022-03-01 | 石家庄学院 | Preparation method of surface-modified functional ceramic-based Bi-based composite photocatalytic material |
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