CN110252381A - A kind of preparation and application of 2D-2D tungstic acid/class graphite phase carbon nitride heterojunction structure photochemical catalyst - Google Patents
A kind of preparation and application of 2D-2D tungstic acid/class graphite phase carbon nitride heterojunction structure photochemical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 3
- 229910002804 graphite Inorganic materials 0.000 title description 3
- 239000010439 graphite Substances 0.000 title description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 title description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title description 2
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 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 claims abstract description 7
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 150000002367 halogens Chemical class 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 238000007146 photocatalysis Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
-
- 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—
-
- 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 2D-2D WO3/g‑C3N4The preparation and application of heterojunction structure photochemical catalyst, the heterojunction structure photochemical catalyst are to prepare two-dimensional g-C using the method for thermal decomposition3N4WO is synthesized as matrix, then by the method for hydro-thermal3Nanometer sheet is to construct the WO of 2D-2D structure3/g‑C3N4Heterojunction structure photochemical catalyst, wherein WO3Mass fraction be 9-17%.The WO3/g‑C3N4Heterojunction structure photochemical catalyst is to be excited (nm of λ >=420) as visible light source using halogen lamp, and which show very high rhodamine B degrading activities, and when light application time continues 40 minutes, the degradation rate of rhodamine B reaches 100%.The composite photo-catalyst preparation method is simple, and easily operated, raw material is cheap, is a kind of clean and effective suitable for industrial application and the lower Organic Waste Water Treatment method of energy consumption.
Description
Technical field
The invention belongs to the preparation fields of catalysis material, and in particular to a kind of 2D-2D WO3/g-C3N4Heterojunction structure light
The preparation and application of catalyst.
Background technique
In photocatalysis field, graphite-phase g-C3N4Because it is a kind of narrow band gap non-metal semiconductive, band gap is about 2.7eV,
There is certain absorption to visible light, and stability is good, structure and performance are easy to regulate and control, there is preferable photocatalysis performance,
Through the concern for causing more and more scientists.g-C3N4It is that there is the stratiform knot of similar graphite using 3-s triazine ring as structural unit
Structure.Wherein, C and N atom is all sp2Hydridization, and the P track of all atoms overlaps each other to form conjugatedπbond, NpTrack
Constitute g-C3N4HOMO track, CpTrack constitutes LUMO track.These properties determine g-C3N4It is that a kind of potential light is urged
Agent.But g-C3N4There is a problem of that photo-generated carrier recombination rate is high, this strongly limits it to be widely popularized.Therefore, many
More researchers is insufficient for this, proposes many modified and modification method, including doping, hybrid inorganic-organic, half
Conductor it is compound and sensitization etc. preparation methods.Wherein, semiconductors coupling is not only only capable of expanding the light abstraction width of wide band gap semiconducter,
The separation and transfer efficiency that photo-generated carrier can also be enhanced, are considered as most effective method of modifying.
Currently, and g-C3N4Compound semiconductor mainly has TiO2、WO3、CdS、Bi2WO6And BiVO4Etc., these are compound
Object is in organic pollutant degradation, production hydrogen or produces oxygen, CO2Reduction etc. illustrates good visible optical property.Tungstic acid
(WO3) it is a kind of cheap and stable transition metal oxide, compared with traditional titanium dioxide optical catalyst, tungsten oxide
It is a kind of more preferably candidate, because it has small band-gap energy (2.7 eV), easily prepared, the nontoxic and sun absorbs effect
Rate is high, high to the photocatalytic activity of water pollutant, and the degradation of especially diazo colours shows significant catalysis energy
Power.WO3There is significant photostability in acidic aqueous solution, it was reported that formic acid and rhodamine B are in WO3Effectively divide on optoelectronic pole
Solve (Photoelectrocatalytic materials for environmental applications. J. Mater.
Chem., 2009,19 (29): 5089-5121.).Therefore, WO3Ideal composite object and g-C can be used as3N4Compound building
High performance visible-light photocatalyst.WO3It is not only only capable of enhancing g-C significantly3N4Efficiency of light absorption, while the hetero-junctions constructed
Structure can also enhance the separation and migration of photo-generated carrier, to improve its light-catalyzed reaction efficiency.
Cui et al. reports WO3/g-C3N4It is living that composite photocatalyst material presents good visible light in terms of the RhB that degrades
Property, RhB degradation rate reaches 100% in 2 hours.(Facile preparation of Z-scheme WO3/g-C3N4
composite photocatalyst with enhanced photocatalytic performance under
Visible light. " Appl. Surf. Sci., 391 (2017): 202-210).Huang et al. has found WO3/g-
C3N4Composite photo-catalyst is under excited by visible light, with pure WO3Or g-C3N4It compares, presents the photocatalytic degradation first of enhancing
The activity of base indigo plant and parachlorophenol, can in 3 hours degradable organic pollutant.(Huang, Liying, et al. "
Visible-light-induced WO3/gC3N4 composites with enhanced photocatalytic
Activity. " Dalton T. 42.24 (2013): 8606-8616.) still, these WO3/g-C3N4Composite photo-catalyst
Photocatalysis efficiency can't reach the requirement of practical application, therefore the stable composite photo-catalyst of synthesizing efficient is still current
One of hot spot of research.Although Li et al. people also constructs the WO of organic inorganic hybridization3/g-C3N4Nanometer sheet compound, but it is base
In the compound synthesized on FTO electro-conductive glass, and g-C3N4It is the compound constructed using the method for dipping calcining, and we
It is to be prepared using the method for a step hydro-thermal, photocatalysis effect affirmative is widely different, and its application field is also different
Sample (Li, Yuangang, et al. " Construction of inorganic-organic 2D/2D WO3/g-C3N4
nanosheet arrays toward efficient photoelectrochemical splitting of natural
Seawater. " Phys. Chem. Chem. Phys. 18.15 (2016): 10255-10261.).
The above research report, illustrates WO3/g-C3N4The preparation and application of compound, and investigated its light-catalysed property
Energy.But the activity of these catalysis materials is investigated, and it is main still to carry out illumination using xenon source, and its photocatalysis is imitated
Rate is also very low, apart from practical application or far.In consideration of it, the present invention provides a kind of WO3Nanometer sheet and stratiform g-C3N4Compound
Preparation, and be applied to photocatalysis degradation organic contaminant.Preparation method of the present invention is simple, easy to operate, is easy to adjust
Control WO3Nanometer sheet and g-C3N4Ratio, and successfully enhance the activity of its photocatalysis degradation organic contaminant.The invention it is excellent
Gesture specific manifestation are as follows: (1) g-C of stratiform is prepared by simple pyrolysismethod3N4, then prepared by the method for a step hydro-thermal
The WO of 2D-2D structure3/g-C3N4Heterojunction structure photochemical catalyst.(2) WO constructed3/g-C3N4Heterojunction structure photochemical catalyst, general
Under logical halogen lamp excitation (nm of λ >=420), excellent Photocatalytic Degradation Property is presented to organic pollutant RhB.(3) the preparation side
Method is relatively easy, and experiment condition is easy to control, and energy consumption is lower, and raw material is cheap, can be used for large batch of production and prepare catalyst, right
Environment is very friendly.
Summary of the invention
The purpose of the invention is to provide a kind of 2D-2D WO3/g-C3N4It the preparation of heterojunction structure photochemical catalyst and answers
With with the g-C of stratiform3N4For matrix, two-dimensional WO is introduced using the method for a step hydro-thermal3Nanometer sheet, building 2D-2D structure
WO3/g-C3N4Heterojunction structure photochemical catalyst, wherein WO3Mass fraction is 9-17%.With single g-C3N4It compares, photocatalysis is living
Property significantly improves, and is in particular under the excitation of common halogen lamp (nm of λ >=420), the WO3/g-C3N4Heterojunction structure photochemical catalyst
The efficient degradable organic pollutant RhB of energy, and it is degradable in 40 minutes, and degradation rate is up to 100%.
Realize that above-mentioned purpose, the present invention adopt the following technical scheme that this:
A kind of 2D-2D WO3/g-C3N4The preparation method of heterojunction structure photochemical catalyst, comprising the following steps:
Step 1: stratiform g-C3N4Preparation
G-C is obtained by thermally decomposing dicyandiamide3N4, specific steps: 5 g dicyandiamides are added into crucible first, then sample
It is placed in Muffle furnace, 500 DEG C of 4 h of calcining is then warming up to the heating rate of 2.3 DEG C/min, after being finally cooled to room temperature
Obtain g-C3N4；
Step 2: 2D-2D WO3/g-C3N4The preparation of heterojunction structure photochemical catalyst
By 0.38-0.73 mmol Na2WO4•2H2O and 1.224 mmol NH4F co-dissolve in 12.5 mL water, then will
12.5 mL HCl (2 mol/L) are slowly dropped into above-mentioned solution, in addition, 1.53 mmol oxalic acid are dissolved in 25 ml water, so
The above-mentioned g-C prepared of 1 g is added afterwards3N4, 1 h, 90 DEG C of 3 h of hydro-thermal reaction is mixed in above two solution, centrifugation is washed
Precipitating is washed, gained is deposited in 60 DEG C of 12 h of drying, is finally warming up to 400- in Muffle furnace with the heating rate of 5 DEG C/min
500 DEG C of 1 h of calcining, obtain WO3/g-C3N4Heterojunction structure photochemical catalyst.
Using: the composite photo-catalyst is applied to Visible Light Induced Photocatalytic organic pollutant rhodamine B, specifically includes as follows
Step: firstly, 80 milligrams of catalyst are added in the RhB solution of 80 milliliter of 10 ppm, lasting stirring and secretly absorption 60 minutes,
To guarantee absorption/desorption equilibrium of catalyst.After secretly adsorbing, halogen lamp illumination is opened.
Remarkable advantage of the invention:
The present invention is directed to existing g-C3N4Catalysis material is asked there are photo-generated carrier recombination rate height and photocatalysis efficiency are low etc.
Topic provides a kind of novel synthetic method, prepares the WO of 2D-2D structure3/g-C3N4Heterojunction structure photochemical catalyst.It is advantageous that
This catalyst has uniform 2D-2D heterojunction structure, under the excited by visible light of common halogen lamp, has very high degradation organic contamination
Ability, when light application time continues 40 minutes, the degradation rate of rhodamine B reaches 100%.Catalyst preparation is easily operated, and raw material is low
It is honest and clean, it can produce in batches, be a kind of clean and effective suitable for industrial application and the lower Organic Waste Water Treatment of energy consumption
Method.
Detailed description of the invention
Fig. 1 is (a) pure g-C3N4(b) 13% WO3/g-C3N4The TEM shape appearance figure of heterojunction structure photochemical catalyst；
Fig. 2 is pure g-C3N4With different content WO3/g-C3N4The XRD spectra of heterojunction structure photochemical catalyst, wherein CNW-9 is corresponding
It is 9%WO3/g-C3N4, CNW-11 corresponding is 11%WO3/g-C3N4, CNW-13 corresponding is 13%WO3/g-C3N4, CNW-15 pairs
That answer is 15%WO3/g-C3N4And it is 17%WO that CNW-17 is corresponding3/g-C3N4Sample；
Fig. 3 is pure g-C3N4With different content WO3/g-C3N4The degradation RhB of heterojunction structure photochemical catalyst schemes.
Specific embodiment
Technical solutions according to the invention are further elaborated below with reference to specific implementation case, but the present invention is not limited to
This.
Embodiment 1
Step 1: g-C is obtained by thermally decomposing dicyandiamide3N4, specific steps: 5 g dicyandiamides are added into crucible first, then
Sample is placed in Muffle furnace, 500 DEG C of 4 h of calcining are then warming up to the heating rate of 2.3 DEG C/min, are finally cooled to
G-C is obtained after room temperature3N4。
80 milligrams of catalyst are added in the RhB solution of 80 milliliter of 10 ppm, lasting stirring and secretly absorption 60 minutes, with
Guarantee absorption/desorption equilibrium of catalyst.After secretly adsorbing, halogen lamp illumination is opened, after at regular intervals, takes 4 milliliters
Reaction solution centrifugation, then takes supernatant to test on ultraviolet-uisible spectrophotometer, experimental result is shown in Table 1.
Embodiment 2
Step 1: g-C is obtained by thermally decomposing dicyandiamide3N4, specific steps: 5 g dicyandiamides are added into crucible first, then
Sample is placed in Muffle furnace, 500 DEG C of 4 h of calcining are then warming up to the heating rate of 2.3 DEG C/min, are finally cooled to
G-C is obtained after room temperature3N4。
Step 2: by 0.38 mmol Na2WO4•2H2O and 1.224 mmol NH4F co-dissolve in 12.5 mL water,
12.5 mL HCl (2 mol/L) are slowly dropped into above-mentioned solution again.In addition, 1.53 mmol oxalic acid are dissolved in 25 ml water
In, the above-mentioned g-C prepared of 1 g is then added3N4, 1 h, 90 DEG C of 3 h of hydro-thermal reaction are mixed in above two solution, from
Heart washing precipitating, gained are deposited in 60 DEG C of 12 h of drying, are finally warming up in Muffle furnace with the heating rate of 5 DEG C/min
500 DEG C of 1 h of calcining, obtain WO3/g-C3N4Heterojunction structure photochemical catalyst.
80 milligrams of catalyst are added in the RhB solution of 80 milliliter of 10 ppm, lasting stirring and secretly absorption 60 minutes, with
Guarantee absorption/desorption equilibrium of catalyst.After secretly adsorbing, halogen lamp illumination is opened, after at regular intervals, takes 4 milliliters
Reaction solution centrifugation, then takes supernatant to test on ultraviolet-uisible spectrophotometer, experimental result is shown in Table 1.
Embodiment 3
Step 1: g-C is obtained by thermally decomposing dicyandiamide3N4, specific steps: 5 g dicyandiamides are added into crucible first, then
Sample is placed in Muffle furnace, 500 DEG C of 4 h of calcining are then warming up to the heating rate of 2.3 DEG C/min, are finally cooled to
G-C is obtained after room temperature3N4。
Step 2: by 0.56 mmol Na2WO4•2H2O and 1.224 mmol NH4F co-dissolve in 12.5 mL water,
12.5 mL HCl (2 mol/L) are slowly dropped into above-mentioned solution again.In addition, 1.53 mmol oxalic acid are dissolved in 25 ml water
In, the above-mentioned g-C prepared of 1 g is then added3N4, 1 h, 90 DEG C of 3 h of hydro-thermal reaction are mixed in above two solution, from
Heart washing precipitating, gained are deposited in 60 DEG C of 12 h of drying, are finally warming up in Muffle furnace with the heating rate of 5 DEG C/min
500 DEG C of 1 h of calcining, obtain WO3/g-C3N4Heterojunction structure photochemical catalyst.
80 milligrams of catalyst are added in the RhB solution of 80 milliliter of 10 ppm, lasting stirring and secretly absorption 60 minutes, with
Guarantee absorption/desorption equilibrium of catalyst.After secretly adsorbing, halogen lamp illumination is opened, after at regular intervals, takes 4 milliliters
Reaction solution centrifugation, then takes supernatant to test on ultraviolet-uisible spectrophotometer, experimental result is shown in Table 1.
Embodiment 4
Specific preparation method and active testing and this part embodiment 2 are essentially identical, the difference is that by 0.38 mmol
Na2WO4•2H2O is changed to 0.47 mmol Na2WO4•2H2O。
Embodiment 5
Specific preparation method and active testing and this part embodiment 2 are essentially identical, the difference is that by 0.38 mmol
Na2WO4•2H2O is changed to 0.65 mmol Na2WO4•2H2O。
Embodiment 6
Specific preparation method and active testing and this part embodiment 2 are essentially identical, the difference is that by 0.38 mmol
Na2WO4•2H2O is changed to 0.73 mmol Na2WO4•2H2O。
Embodiment 7
Specific preparation method and active testing and this part embodiment 3 are essentially identical, the difference is that by the calcining of step 2
Temperature is changed to 450 DEG C by 500 DEG C.
Embodiment 8
Specific preparation method and active testing and this part embodiment 3 are essentially identical, the difference is that by the calcining of step 2
Temperature is changed to 400 DEG C by 500 DEG C.
The degradation rate of the rhodamine B of 1 different catalysts of table
It is as shown in Figure 1 pure g-C3N4With 13% WO3/g-C3N4The TEM shape appearance figure of heterojunction structure photochemical catalyst, it can be deduced that pure
g-C3N4It is exactly the pattern of two-dimensional layer, and introduces WO3Afterwards, in g-C3N4There is WO in surface3Nanometer sheet illustrates successfully to be prepared for
2D-2D WO3/g-C3N4Heterojunction structure photochemical catalyst.
As shown in Fig. 2, having investigated g-C3N4With different content WO3/g-C3N4The crystal structure of heterojunction structure photochemical catalyst.
XRD spectra illustrates pure g-C3N4And WO3/g-C3N4The diffraction maximum of sample.Obviously, WO3/g-C3N4Sample in 23.1o, 23.6o and
There is new diffraction maximum in the position of 24.4o, they are to belong to WO respectively3Crystal (JCPDS No. 43-1035) (002),
(020) and WO is successfully prepared in the crystal face of (200), further explanation3/g-C3N4Composite material.
As shown in figure 3, having investigated g-C in embodiment 1,2,3,4,5 and 63N4With different content WO3/g-C3N4The light of sample
Catalytic degradation organic pollutant activity, illustrates the WO of preparation3/g-C3N4Heterogeneous Composite photochemical catalyst has outstanding photocatalysis
Degradation property especially works as WO3Content be 13% when, at continuous light 40 minutes of halogen lamp, photocatalytic degradation efficiency reached
100%。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (3)
1. a kind of 2D-2D WO3/g-C3N4The preparation method of heterojunction structure photochemical catalyst, it is characterised in that: with the g- of two-dimensional layer
C3N4For matrix, then the method introducing WO using a step hydro-thermal3Nanometer sheet constructs the WO of 2D-2D structure3/g-C3N4Heterogeneous Composite
Photochemical catalyst, wherein WO3Mass fraction be 9-17 %.
2. a kind of 2D-2D WO according to claim 13/g-C3N4The preparation method of heterojunction structure photochemical catalyst, feature
It is, specifically comprises the following steps:
Step 1: stratiform g-C3N4Preparation
G-C is obtained by thermally decomposing dicyandiamide3N4, specific steps: 5 g dicyandiamides are added into crucible first, then sample is put
It sets in Muffle furnace, 500 DEG C of 4 h of calcining is then warming up to the heating rate of 2.3 DEG C/min, obtained after being finally cooled to room temperature
To g-C3N4；
Step 2: 2D-2D WO3/g-C3N4The preparation of heterojunction structure photochemical catalyst
By 0.38-0.73 mmol Na2WO4•2H2O and 1.224 mmol NH4F co-dissolve is in 12.5 mL water, then by 12.5
The HCl solution of 2 mol/L of mL is slowly dropped into above-mentioned solution, in addition, 1.53 mmol oxalic acid are dissolved in 25 ml water, then
The above-mentioned g-C prepared of 1 g is added3N4, 1 h, 90 DEG C of 3 h of hydro-thermal reaction, centrifuge washing is mixed in above two solution
Precipitating, gained are deposited in 60 DEG C of 12 h of drying, are finally warming up to 400-500 in Muffle furnace with the heating rate of 5 DEG C/min
DEG C calcining 1 h, obtain WO3/g-C3N4Heterojunction structure photochemical catalyst.
3. WO made from a kind of preparation method as claimed in claim 1 or 23/g-C3N4The application of heterojunction structure photochemical catalyst,
It is characterized by: the WO3/g-C3N4Heterojunction structure photocatalyst applications are in Visible Light Induced Photocatalytic organic pollutant rhodamine B.
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