CN108554438A - A kind of g-C3N4- Ag crystal faces BiVO4Z-type structure photochemical catalyst and preparation method thereof - Google Patents
A kind of g-C3N4- Ag crystal faces BiVO4Z-type structure photochemical catalyst and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 101
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 239000006228 supernatant Substances 0.000 claims abstract description 20
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000031700 light absorption Effects 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- -1 i.e. Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000012719 thermal polymerization Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000008859 change Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction 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
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of g C3N4Ag crystal faces BiVO4The preparation method of Z-type structure photochemical catalyst.Hydro-thermal method prepares the surface heterogeneous medium knot BiVO of (010) exposure crystal face4, ultrasonic disperse prepares thermal polymerization method g C3N4Supernatant.By BiVO4、AgNO3、g‑C3N4Supernatant is stirred by ultrasonic to form precursor liquid, its photoreduction is prepared coralliform g C3N4Ag (010) crystal face BiVO4Z-type structure photochemical catalyst.Photochemical catalyst is increased near infrared region light absorption, improves the redox ability of photochemical catalyst, makes photocatalysis performance enhancing of the photochemical catalyst under visible region and near infrared region.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of g-C3N4- Ag- (010) crystal face BiVO4Z-type structure light is urged
Agent and preparation method thereof.
Background technology
BiVO4As a kind of novel semiconductor material, band gap is narrow (2.4eV or so), has outstanding visible light-responded, leads
Band and valence band location (contrast standard hydrogen electrode) are suitable, be have simultaneously photodissociation aquatic products oxygen, reduction, degradation of contaminant ability one
The effective semiconductor light-catalyst of kind.However BiVO4That there are specific surface areas is small for catalyst, light quantum utilization rate is low, electrons and holes
The problems such as recombination probability is high, absorption property is poor, photo-generated carrier is difficult to migrate, researcher propose to improve by two aspects
BiVO4Photocatalysis performance, when improve BiVO4The activity of itself such as improves crystallinity, improves pattern, increases high activity crystal face
Exposure etc..(010) crystal face of wherein monoclinic phase pucherite provides polyatom BiVO4Center, it may be possible to which photocatalysis produces oxygen and lives
Property point origin be particularly helpful to the generation of catalyst surface oxide of high activity active specy OH, improve degradation rate；Second is that right
BiVO4Be modified as：Metal deposit, nonmetal doping, surface modification, with organic matter hydridization, semiconductors coupling etc.；Wherein,
The separation rate of photo-generated carrier can be improved by forming effective hetero-junctions by semiconductors coupling, enhance 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 composed structure unit on its layer can be by
C3N3Or C6N7It constitutes.g-C3N4Conduction band be by C atoms pzTrack forms, and conduction band positions are about -1.30eV；And valence
Band is then by the p of N atomsZTrack forms, and valence band location is about 1.40eV, g-C3N4Band gap width between valence conduction band is
2.70eV。
Invention content
The purpose of the present invention is to provide a kind of g-C3N4- Ag crystal faces BiVO4Z-type structure photochemical catalyst and preparation method thereof,
Compound using the progress of photoreduction method, the more other chemical synthesis of technological process are simple, are successfully prepared out Z-type structure g-C3N4-
Ag- (010) crystal face BiVO4Photochemical catalyst makes photochemical catalyst enhance in the photocatalysis performance of visible region and near infrared region.
In order to achieve the above object, preparation method of the invention includes the following steps：
Step 1, by Bi (NO3)3·5H2O is dissolved in dilute HNO3In, 10~50min is stirred, NH is then added4VO3, stirring 80
~140min forms precursor liquid A；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:Bi in 1, precursor liquid A3+It is dense
Degree is 0.1~0.3mol/L；
Step 2, by precursor liquid A, 13~16h of hydro-thermal reaction, reaction terminate at 70~90 DEG C, by precipitated product washing, do
It is dry, obtain (010) crystal face BiVO4Powder；
Step 3, by CO (NH2)2530~580 DEG C are raised to from room temperature with 8~15 DEG C/min heating rates, keeps the temperature 2~4h,
Class graphitic nitralloy carbon g-C is made3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.001~0.03g/mL is obtained in deionized water3N4Solution surpasses
After sound decentralized processing, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO45%~30% by AgNO3With prepare
(010) crystal face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality
With (010) crystal face BiVO of addition4Powder and AgNO3Quality sum ratio be (2~11):(11~2)；
Step 6, sedimentation is selected to be placed in illumination 2 in ultraviolet light environments under agitation with photoreduction precursor liquid B
After~8h, g-C is obtained after washing, drying3N4- Ag- (010) crystal face BiVO4Photochemical catalyst.
Drying in the step 2 and step 6 is in 60~80 DEG C of 8~10h of freeze-day with constant temperature.
Step 4 ultrasonic time is 1~3h, and ultrasonic power is 80~100W.
By coralliform g-C made from method made above3N4- Ag- (010) crystal face BiVO4Z-type structure photochemical catalyst, light are urged
BiVO in agent4For the monoclinic phase of exposure (010) crystal face and (110) crystal face, space structure group is the surface heterogeneous medium knot of I2/a
BiVO4, Ag first selects to deposit to BiVO4(010) on exposure crystal face, then by electrostatic force by class graphitic nitralloy carbon (g-C3N4) with
The BiVO of loaded Ag4(010) exposure crystal face is compound, forms coralliform Z-type structure g-C3N4- Ag- (010) crystal face BiVO4Light is urged
Agent.
The surface plasma resonance effect of the Ag makes composite photo-catalyst have in 750~1500nm of near infrared region
Stronger light absorption, and Ag is Z-type structure g-C3N4- Ag- (010) crystal face BiVO4The electron mediator of photochemical catalyst, i.e., Ag is in g-
C3N4(010) crystal face BiVO4Between.
Z-type structure photochemical catalyst photocurrent response intensity under near infrared light is (010) crystal face BiVO4Photo-current intensity
9.12 times, Z-type structure photochemical catalyst has the application under visible region and near infrared region in terms of catalytic degradation organic matter.
Compared with prior art, the invention has the advantages that：
G-C provided by the invention3N4- Ag- (010) crystal face BiVO4The preparation method of Z-type structure photochemical catalyst.Use hydro-thermal method
Prepare (010) crystal face BiVO4, ultrasonic disperse processing calcining urea prepared by g-C3N4, take its supernatant.Then by BiVO4、
AgNO3、g-C3N4Supernatant mixing that treated, prepares Z-type structure photochemical catalyst under Hg lamp irradiation.The shape of Z-type structure
At having blocked compound and back reaction the generation in light induced electron-hole pair, while photochemical catalyst redox ability is improved,
Near infrared region light absorption is increased, BiVO is improved4In visible region and near infrared region photocatalysis performance.
Description of the drawings
G-C prepared by Fig. 1 present invention3N4- Ag- (010) crystal face BiVO4The XRD of Z-type structure photochemical catalyst is composed
Fig. 2 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4Z-type structure photochemical catalyst SEM figures
Fig. 3 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4The UV-NIR DRS of Z-type structure photochemical catalyst
Figure
Fig. 4 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4Drop of the Z-type structure photochemical catalyst under sunlight
Xie Tu
Fig. 5 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4Z-type structure photochemical catalyst is under near infrared light
Photoelectric current collection of illustrative plates.
Specific implementation mode
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 Bi (NO3)3·5H2O is dissolved in dilute HNO of a concentration of 1mol/L3In, it is added after stirring 30min
NH4VO3, 120min is stirred, precursor liquid A is formed；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:In 1, precursor liquid A
Bi3+A concentration of 0.1mol/L；
Step 2, by precursor liquid A at 70 DEG C hydro-thermal reaction 15h, after reaction, by washing of precipitate, 70 DEG C of freeze-day with constant temperature
9h is exposed the monoclinic phase of (010) crystal face and (110) crystal face, and space structure group is the BiVO of I2/a4Surface heterogeneous medium knot powder；
Step 3, by CO (NH2)2550 DEG C are raised to from room temperature with 15 DEG C/min heating rates, keeps the temperature 4h, class graphite nitrogen is made
Change carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.01g/mL is obtained in deionized water3N4Solution, power 80
After 1~3h of~100W ultrasonic disperses, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO415% by AgNO3With (010) crystalline substance prepared
Face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be 10:2.9；
Step 6, sedimentation is selected to be placed under agitation in ultraviolet light environments in power with photoreduction precursor liquid B
After 2~8h of mercury lamp illumination of 500W, g-C is obtained after washing, 70 DEG C of freeze-day with constant temperature 9h3N4- Ag- (010) crystal face BiVO4Light
Catalyst.
Embodiment 2：
Step 1：By Bi (NO3)3·5H2O is dissolved in dilute HNO of a concentration of 1mol/L3In, it is added after stirring 10min
NH4VO3, 100min is stirred, precursor liquid A is formed；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:In 1, precursor liquid A
Bi3+A concentration of 0.2mol/L；
Step 2, by precursor liquid A at 80 DEG C hydro-thermal reaction 14h, after reaction, by washing of precipitate, 60 DEG C of freeze-day with constant temperature
10h is exposed the monoclinic phase of (010) crystal face and (110) crystal face, and space structure group is the BiVO of I2/a4Surface heterogeneous medium knot powder
Body；
Step 3, by CO (NH2)2530 DEG C are raised to from room temperature with 10 DEG C/min heating rates, keeps the temperature 4h, class graphite nitrogen is made
Change carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.006g/mL is obtained in deionized water3N4Solution, power 80
After 1~3h of~100W ultrasonic disperses, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO45% by AgNO3With (010) crystal face prepared
BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be 11:2；
Step 6, sedimentation is selected to be placed under agitation in ultraviolet light environments in power with photoreduction precursor liquid B
After 2~8h of mercury lamp illumination of 500W, g-C is obtained after washing, 60 DEG C of freeze-day with constant temperature 10h3N4- Ag- (010) crystal face BiVO4Light
Catalyst.
Embodiment 3：
Step 1：By Bi (NO3)3·5H2O is dissolved in dilute HNO of a concentration of 2mol/L3In, it is added after stirring 50min
NH4VO3, 140min is stirred, precursor liquid A is formed；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:In 1, precursor liquid A
Bi3+A concentration of 0.3mol/L；
Step 2, by precursor liquid A at 85 DEG C hydro-thermal reaction 13h, after reaction, by washing of precipitate, 80 DEG C of freeze-day with constant temperature
8h is exposed the monoclinic phase of (010) crystal face and (110) crystal face, and space structure group is the BiVO of I2/a4Surface heterogeneous medium knot powder；
Step 3, by CO (NH2)2560 DEG C are raised to from room temperature with 12 DEG C/min heating rates, keeps the temperature 3h, class graphite nitrogen is made
Change carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.009g/mL is obtained in deionized water3N4Solution, power 80
After 1~3h of~100W ultrasonic disperses, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO420% by AgNO3With (010) crystalline substance prepared
Face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be 6:4；
Step 6, sedimentation is selected to be placed under agitation in ultraviolet light environments in power with photoreduction precursor liquid B
After 2~8h of mercury lamp illumination of 500W, g-C is obtained after washing, 80 DEG C of freeze-day with constant temperature 8h3N4- Ag- (010) crystal face BiVO4Light
Catalyst.
Embodiment 4：
Step 1：By Bi (NO3)3·5H2O is dissolved in dilute HNO of a concentration of 2mol/L3In, it is added after stirring 20min
NH4VO3, 80min is stirred, precursor liquid A is formed；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:In 1, precursor liquid A
Bi3+A concentration of 0.15mol/L；
Step 2, by precursor liquid A at 75 DEG C hydro-thermal reaction 16h, after reaction, by washing of precipitate, 75 DEG C of freeze-day with constant temperature
9.5h is exposed the monoclinic phase of (010) crystal face and (110) crystal face, and space structure group is the BiVO of I2/a4Surface heterogeneous medium knot powder
Body；
Step 3, by CO (NH2)2580 DEG C are raised to from room temperature with 8 DEG C/min heating rates, keeps the temperature 2h, class graphitic nitralloy is made
Carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.03g/mL is obtained in deionized water3N4Solution, power 80
After 1~3h of~100W ultrasonic disperses, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO410% by AgNO3With (010) crystalline substance prepared
Face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be 3:1；
Step 6, sedimentation is selected to be placed under agitation in ultraviolet light environments in power with photoreduction precursor liquid B
After 2~8h of mercury lamp illumination of 500W, g-C is obtained after washing, 75 DEG C of freeze-day with constant temperature 9.5h3N4- Ag- (010) crystal face BiVO4
Photochemical catalyst.
Embodiment 5：
Step 1：By Bi (NO3)3·5H2O is dissolved in dilute HNO of a concentration of 3mol/L3In, it is added after stirring 40min
NH4VO3, 130min is stirred, precursor liquid A is formed；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:In 1, precursor liquid A
Bi3+A concentration of 0.25mol/L；
Step 2, by precursor liquid A at 90 DEG C hydro-thermal reaction 15h, after reaction, by washing of precipitate, 65 DEG C of freeze-day with constant temperature
8.5h is exposed the monoclinic phase of (010) crystal face and (110) crystal face, and space structure group is the BiVO of I2/a4Surface heterogeneous medium knot powder
Body；
Step 3, by CO (NH2)2540 DEG C are raised to from room temperature with 13 DEG C/min heating rates, keeps the temperature 4h, class graphite nitrogen is made
Change carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.015g/mL is obtained in deionized water3N4Solution, power 80
After 1~3h of~100W ultrasonic disperses, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO425% by AgNO3With (010) crystalline substance prepared
Face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be 1:1；
Step 6, sedimentation is selected to be placed under agitation in ultraviolet light environments in power with photoreduction precursor liquid B
After 2~8h of mercury lamp illumination of 500W, g-C is obtained after washing, 65 DEG C of freeze-day with constant temperature 9h3N4- Ag- (010) crystal face BiVO4Light
Catalyst.
Embodiment 6：
Step 1：By Bi (NO3)3·5H2O is dissolved in dilute HNO of a concentration of 3mol/L3In, it is added after stirring 50min
NH4VO3, 90min is stirred, precursor liquid A is formed；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:In 1, precursor liquid A
Bi3+A concentration of 0.3mol/L；
Step 2, by precursor liquid A at 80 DEG C hydro-thermal reaction 15h, after reaction, by washing of precipitate, 70 DEG C of freeze-day with constant temperature
10h is exposed the monoclinic phase of (010) crystal face and (110) crystal face, and space structure group is the BiVO of I2/a4Surface heterogeneous medium knot powder
Body；
Step 3, by CO (NH2)2570 DEG C are raised to from room temperature with 10 DEG C/min heating rates, keeps the temperature 2h, class graphite nitrogen is made
Change carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.001g/mL is obtained in deionized water3N4Solution, power 80
After 1~3h of~100W ultrasonic disperses, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO430% by AgNO3With (010) crystalline substance prepared
Face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be 2:11；
Step 6, sedimentation is selected to be placed under agitation in ultraviolet light environments in power with photoreduction precursor liquid B
After 2~8h of mercury lamp illumination of 500W, g-C is obtained after washing, 70 DEG C of freeze-day with constant temperature 9h3N4- Ag- (010) crystal face BiVO4Light
Catalyst.
Fig. 1 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4The XRD diffraction patterns of Z-type structure photochemical catalyst
Spectrum, g-C3N4-Ag-BiVO4Photochemical catalyst has apparent diffraction maximum in the angle of diffraction 35.26,40.098,50.36,53.50 etc.,
(011), (112), (004), (020), (211), (220), (116) crystal face of corresponding monoclinic phase, monoclinic phase BiVO4Feature
Peak diffraction locations, width do not change, it is meant that Ag and g-C3N4Introducing to BiVO4Phase structure do not influence.It can be with
It was found that g-C3N4-Ag-BiVO4Composite photo-catalyst has apparent g-C in 2 θ=27.76 °3N4Diffraction maximum has at 2 θ=38.16 °
Apparent Ag diffraction maximums.This shows successfully to have prepared g-C3N4- Ag- (010) crystal face BiVO4Photochemical catalyst.
It is g-C in Fig. 23N4- Ag- (010) crystal face BiVO4Z-type structure photochemical catalyst SEM figures.
g-C3N4-Ag-BiVO4For closely coupled coralliform structure, the BiVO as schemed marked prism-frustum-shaped4And lamella
The g-C of shape3N4.Do not see that Ag is deposited on BiVO4(010) active crystal face on, but XRD diffraction pattern analysis shows Ag successes
Introduce g-C3N4-Ag-BiVO4In composite photo-catalyst, thus speculate in g-C3N4-Ag-BiVO4In composite photo-catalyst, Ag is heavy
Product is in g-C3N4And BiVO4Between crystal face.
Fig. 3 is g-C prepared by different process3N4- Ag- (010) crystal face BiVO4The UV-NIR of Z-type structure photochemical catalyst
DRS schemes.B and c is respectively the g-C prepared according to embodiment 2 and 33N4- Ag- (010) crystal face BiVO4The UV-NIR of photochemical catalyst
DRS schemes.From the graph, it is apparent that g-C3N4-Ag-BiVO4Sample has strong absorption in ultraviolet-visible light area, is conducive to
The raising of absorption and photocatalytic activity to visible light.Loaded Ag and g-C3N4Afterwards, blue shift has occurred in Absorption edge, and increases
Visible light and near infrared region (750~1500nm) light absorption, illustrate loaded Ag and g-C3N4After can enhance g-C3N4-Ag-BiVO4
Visible absorption, and light abstraction width can be spread near infrared region.
Fig. 4 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4Drop of the Z-type structure photochemical catalyst under sunlight
Xie Tu.Wherein a, c are respectively the g-C prepared according to embodiment 1,33N4- Ag- (010) crystal face BiVO4Photochemical catalyst is being simulated too
The degradation curve of rhodamine B degradation, g-C under sunlight3N4-Ag-BiVO410:2.9 and g-C3N4-Ag/BiVO46:4 degradation rate
Respectively 33.9%, 70.5%, it is pure BiVO41.62 times, 3.37 times.This shows compound Ag and g-C3N4After improve pure phase
BiVO4Catalytic efficiency under sunlight improves pure phase BiVO4Photocatalysis performance,
Fig. 5 is g-C prepared by the present invention3N4- Ag- (010) crystal face BiVO4Z-type structure photochemical catalyst is under near infrared light
Photoelectric current collection of illustrative plates.Wherein b is the g-C prepared according to embodiment 23N4- Ag- (010) crystal face BiVO4Photochemical catalyst.It can from figure
It arrives, g-C3N4- Ag- (010) crystal face BiVO4Z-type structure photochemical catalyst near infrared light photograph under its photocurrent response intensity be
1.738×10-1μ A, (010) crystal face BiVO4Photo-current intensity be 1.906 × 10-2μ A, Z-type structure photochemical catalyst is close red
Photocurrent response intensity is (010) crystal face BiVO under outer light49.12 times of photo-current intensity, this shows compound Ag and g-C3N4
After improve pure phase BiVO4Catalytic efficiency under near infrared light, g-C3N4- Ag- (010) crystal face BiVO4Z-type structure photocatalysis
Agent has photocatalytic activity under near infrared light.
The foregoing is merely one embodiment of the present invention, it is not all of or unique embodiment, this field is common
Any equivalent transformation that technical staff takes technical solution of the present invention by reading description of the invention, is the present invention
Claim covered.
Claims (7)
1. a kind of g-C3N4- Ag crystal faces BiVO4The preparation method of Z-type structure photochemical catalyst, which is characterized in that include the following steps：
Step 1：By Bi (NO3)3·5H2O is dissolved in dilute HNO3In, add NH after stirring 10~50min4VO3, stirring 80~
140min forms precursor liquid A；Wherein Bi (NO3)3·5H2O and NH4VO3Molar ratio be 1:Bi in 1, precursor liquid A3+Concentration
For 0.1~0.3mol/L；
Step 2, by precursor liquid A, 13~16h of hydro-thermal reaction by washing of precipitate, drying, is obtained after reaction at 70~90 DEG C
To (010) crystal face BiVO4Powder；
Step 3, by CO (NH2)2530~580 DEG C are raised to from room temperature with 8~15 DEG C/min heating rates, keeps the temperature 2~4h, class is made
Graphitic nitralloy carbon g-C3N4Powder；
Step 4, by g-C3N4Powder is dissolved in the g-C that a concentration of 0.001~0.03g/mL is obtained in deionized water3N4Solution, ultrasound point
After dissipating processing, its supernatant is taken；
Step 5, under agitation, by AgNO3Quality be BiVO45%~30% by AgNO3With (010) crystalline substance prepared
Face BiVO4Powder is added in the supernatant of step 4, obtains precursor liquid B, wherein g-C3N4G-C in solution3N4Quality be added
(010) crystal face BiVO4Powder and AgNO3Quality sum ratio be (2~11):(11~2)；
Step 6, sedimentation is selected to be placed in 2~8h of illumination in ultraviolet light environments under agitation with photoreduction precursor liquid B
Afterwards, it washs, obtain g-C after drying3N4- Ag- (010) crystal face BiVO4Photochemical catalyst.
2. g-C according to claim 13N4- Ag crystal faces BiVO4The preparation method of Z-type structure photochemical catalyst, feature exist
In the drying in the step 2 and step 6 is in 60~80 DEG C of 8~10h of freeze-day with constant temperature.
3. g-C according to claim 13N4- Ag crystal faces BiVO4The preparation method of Z-type structure photochemical catalyst, feature exist
In step 4 ultrasonic time is 1~3h, and ultrasonic power is 80~100W.
4. g-C according to claim 13N4- Ag crystal faces BiVO4The preparation method of Z-type structure photochemical catalyst, feature exist
In mercury lamp power used in photoreduction method is 500W in the step 6.
5. g-C made from a kind of preparation method according to claim 13N4- Ag crystal faces BiVO4Z-type structure photochemical catalyst,
It is characterized in that, BiVO in the photochemical catalyst4For the monoclinic phase of exposure (010) crystal face and (110) crystal face, space structure group is
The surface heterogeneous medium knot BiVO of I2/a4, Ag first selects to deposit to BiVO4(010) on exposure crystal face, then by electrostatic force by class graphite
Carbonitride (g-C3N4) with the BiVO of loaded Ag4(010) exposure crystal face is compound, forms coralliform Z-type structure g-C3N4-Ag-(010)
Crystal face BiVO4Photochemical catalyst.
6. g-C according to claim 53N4- Ag crystal faces BiVO4Z-type structure photochemical catalyst, which is characterized in that the Ag
Surface plasma resonance effect make composite photo-catalyst that there is stronger light absorption, and Ag in 750~1500nm of near infrared region
For Z-type structure g-C3N4- Ag- (010) crystal face BiVO4The electron mediator of photochemical catalyst, i.e., Ag is in g-C3N4(010) crystal face
BiVO4Between.
7. g-C according to claim 53N4- Ag crystal faces BiVO4Z-type structure photochemical catalyst, it is characterised in that：Z-type structure
Photochemical catalyst photocurrent response intensity under near infrared light is (010) crystal face BiVO49.12 times of photo-current intensity, Z-type knot
Structure photochemical catalyst has the application in terms of catalytic degradation organic matter under visible region and near infrared region.
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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 |
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| CN109622013B (en) * | 2018-12-07 | 2021-06-01 | 陕西科技大学 | Graphite-like carbon nitride- (110) crystal face bismuth vanadate Z-type heterojunction photocatalyst and preparation method and application thereof |
| CN110426428A (en) * | 2019-07-30 | 2019-11-08 | 山东农业大学 | Optical electro-chemistry sensor based on Ti-MOF detects N1The method of methyl adenine |
| CN111992239A (en) * | 2020-09-22 | 2020-11-27 | 陕西科技大学 | Silver/bismuth vanadate/carbon nitride heterojunction photocatalyst and preparation method and application thereof |
| CN111992239B (en) * | 2020-09-22 | 2022-08-30 | 陕西科技大学 | Silver/bismuth vanadate/carbon nitride heterojunction photocatalyst and preparation method and application thereof |
| CN113896243A (en) * | 2021-09-29 | 2022-01-07 | 陕西科技大学 | BiVO4Nanosheet and preparation method and application thereof |
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