CN106076382A - A kind of preparation method and application of coordinated compound/carbonitride composite photo-catalyst - Google Patents
A kind of preparation method and application of coordinated compound/carbonitride composite photo-catalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000003403 water pollutant Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 acids Salt Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003517 fume Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005263 ab initio calculation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 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
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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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention discloses the preparation method and application of coordinated compound/carbonitride composite photo-catalyst, by coordinated compound and g C3N4Composition, the mass fraction of described coordinated compound (HW) is 5wt%～20wt%, described g C3N4Mass fraction be 80wt%～95wt%；Compared with prior art, the present invention improves light utilization ratio, solves the water miscible defect of coordinated compound, improves g C3N4The defects such as quantum efficiency is low, thus improve photocatalysis efficiency.Preparation method is simple, low cost, beneficially industrialized production.Experiment shows, this inventive method the HW/g C prepared3N4Composite photo-catalyst has efficient visible light photocatalytic degradation water pollutant performance, and the purer carbonitride of degradation rate is improved largely.
Description
Technical field
The invention belongs to photocatalysis technology field, particularly relate to a kind of coordinated compound/carbonitride composite photo-catalyst
Preparation method and application.
Background technology
Along with appearance and the deterioration of global environment, the energy and the environment of energy crisis are 21 century facing mankinds and urgently solve
Significant problem certainly.Solar energy is a kind of regenerative resource, has the advantages such as inexhaustible, cleanliness without any pollution.Light
Catalysis technique is as a kind of " green " technology, it is possible to use sunlight, as light source, can be not only used for processing asking of water pollution
Topic, but also may be used for processing the many aspects such as atmospheric pollution, soil pollution, sterilization, show the most wide application
It is worth (Chem.Rev.2014,114,9919-9986).
In recent years, polyoxometallate (POM) has as one and TiO2The molecular material of identity function causes people
Great interest, research shows, POM also has preferable photocatalysis performance.Organic contamination in research and development POM photocatalytic degradation water
The green light catalyst of thing has high using value.POM light-catalyzed reaction, it is simply that absorb photon generation electronics with POM and jump
Move initiation, at O2In the presence of, the 2p electronics in oxygen atom is to the 5d unoccupied orbital transition of transition metal M, i.e. the electric charge of O → M turns
Moving transition (OMCT), according to molecular orbital theory, after POM absorbing light, the electronics in its molecule is by highest occupied molecular orbital
(HOMO) it is excited to the minimum track (LUMO) that do not occupies, forms the POM of excited state*, POM*There is stronger oxidability, can
Formation heteropoly blue POM self it is reduced to aoxidize other material-(Appl Catal B:Environ 2013,138–139,
446–452).Especially, sodium decatungstate (Na4W10O32) extremely close in terms of Industrial Wastewater Treatment with its high-quantum efficiency
Note, it is possible to by organic pollutants particularly C-X (X=Cl, Br, I) key scission of link thus reach degraded purpose
(Chem.Soc.Rev.,2009,38,2609–2621；Chemosphere 2011,85,558–564).But, same to TiO2One
Sample, Na4W10O32The efficiency of light energy utilization is low, only with ultraviolet light, and accounts for the visible light part (energy of the overwhelming majority in solar spectrum
Amount accounts for 45%) it is not utilized effectively, thus hinder its actual application.On the other hand, Na4W10O32Have higher water-soluble
Property, it is difficult to recycle, be lost in reaction system to cause environmental pollution (Chem.Commun., 2010,46,2,429 2431；
J.Catal.,2008,253,312–317)。
Graphite phase carbon nitride g-C in recent years3N4Due to its excellence chemical stability, special electronic band structure, do not contain
Metal component, the feature such as visible light-responded is caused the great interest of research worker, due to g-C3N4There is the highest exciton combine
Energy and relatively low-crystallinity, be unfavorable for fast transferring and the high efficiency separation of photo-generate electron-hole pair, thus cause its photocatalytic process
There is the deficiencies such as photo-generate electron-hole is compound serious, quantum efficiency is low, its extensive at the energy and environmental area of serious restriction
Popularization and application (ACS Appl.Mater.Interfaces 2014,6,16449-16465；ACS Catal.2012,2,1596-
1606)。
Accordingly, it is considered to arrive Na4W10O32And g-C3N4Pluses and minuses, by the two combine preparation complex-coordinated compound/
Carbonitride (HW/g-C3N4), on the one hand improve light utilization ratio, on the other hand efficiently solve Na4W10O32Water miscible scarce
Fall into, and the heterojunction structure being compounded to form can be effectively improved g-C3N4Compound serious, the quantum effect of the photo-generate electron-hole existed
Rate is low waits deficiency.It is currently based on Na4W10O32With g-C3N4Build photocatalysis composite and be applied to environmental contaminants
There is not been reported for photocatalytic degradation.
Summary of the invention
The purpose of the present invention is that provides a kind of HW/g-C to solve the problems referred to above3N4The system of composite photo-catalyst
Preparation Method and application.
The present invention is achieved through the following technical solutions above-mentioned purpose:
The present invention is by HW and g-C3N4Composition, the mass fraction of described HW is 5wt%～20wt%, described g-C3N4Matter
Amount mark is 80wt%～95wt%, and its concrete preparation method comprises the following steps:
(1) in 250mL round-bottomed flask, 0.01mol (3.3g) Na it is sequentially added into2WO4·2H2O and 4mL H2O, boils
5min, adds 6.9mL 3M HCl, is being stirred continuously lower addition and is dissolved in 0.003mol (1.46g) cetyl of 4mL water/ethanol
Trimethylammonium bromide (CTAB), maintains the temperature at 100 DEG C, and reflux 10min, and reaction is produced by deionized water/washing with alcohol after terminating
Thing, 50 DEG C are dried；
(2) tripolycyanamide is placed in the crucible added a cover, in Muffle furnace, is warming up to 550 with the programming rate of 2.3 DEG C/min
DEG C, keeping 4h, after natural cooling, the yellow powder of gained is block g-C3N4；
(3) by step (1), HW and g-C of (2) gained3N4It is scattered in respectively in 50mL methanol, ultrasonic 1h, suspension is mixed
Close and ultrasonic be placed in fume hood volatilization 2h, after methanol solution volatilization is dry, i.e. obtain by HW and g-C3N4The photocatalyst being composited
(HW/g-C3N4Composite photo-catalyst).
Preferably, the mass fraction of described HW is 8wt%, described g-C3N4Mass fraction be 92wt%.
HW/g-C prepared by technique scheme3N4Composite photo-catalyst is used for visible light photocatalytic degradation water pollutant.
The beneficial effects of the present invention is:
The present invention is the preparation method and application of a kind of coordinated compound/carbonitride composite photo-catalyst, with prior art
Comparing, the present invention is effectively improved light utilization ratio, solves Na4W10O32Water miscible defect, improves g-C3N4Quantum
Efficiency is low waits deficiency, thus improves photocatalysis efficiency.Preparation method is simple, low cost, beneficially industrialized production.Experiment table
Bright, that prepare for this inventive method HW/g-C3N4Composite photo-catalyst has efficient visible light photocatalytic degradation water pollutant
Can, degradation rate relatively g-C3N4It is improved largely.
Accompanying drawing explanation
Fig. 1 is embodiment 1～the HW/g-C of example 3 preparation3N4Composite photo-catalyst and pure HW and g-C3N4X-ray
Diffraction (XRD) spectrogram；
Fig. 2 a is embodiment 1 and the HW/g-C of example 3 preparation3N4Composite photo-catalyst and pure HW and g-C3N4Infrared
Spectrum (FTIR) spectrogram；
Fig. 2 b is the enlarged drawing of Fig. 2 a；
Fig. 3 a-3d is the HW/g-C of embodiment 1 preparation3N4Scanning electron microscope (SEM) photo of composite photo-catalyst,
Fig. 3 a is g-C3N4, Fig. 3 b be HW, Fig. 3 c, Fig. 3 d be 8wt%HW/g-C3N4；
Fig. 4 a-4d is the HW/g-C of embodiment 1 preparation3N4Transmission electron microscope (TEM) photo of composite photo-catalyst,
Fig. 4 a is g-C3N4, Fig. 4 b be HW, Fig. 4 c, Fig. 4 d be 8wt%HW/g-C3N4；
Fig. 5 is embodiment 1～the HW/g-C of example 3 preparation3N4Composite photo-catalyst and pure HW and g-C3N4Ultraviolet-
Visible diffuse-reflectance spectrum (UV-DRS) spectrogram；
Fig. 6 is embodiment 1～the HW/g-C of example 3 preparation3N4Composite photo-catalyst and pure HW and g-C3N4In the presence of
Methyl orange (MO) degradation curve.
Detailed description of the invention
The invention will be further described below in conjunction with the accompanying drawings:
The present invention is by HW and g-C for embodiment 13N4Composition, the mass fraction of described HW is 5wt%～20wt%, described g-
C3N4Mass fraction be 80wt%～95wt%, its concrete preparation method comprises the following steps:
(1) in 250mL round-bottomed flask, 0.01mol (3.3g) Na it is sequentially added into2WO4·2H2O and 4mL H2O, boils
5min, adds 6.9mL 3M HCl, is being stirred continuously lower addition and is dissolved in 0.003mol (1.46g) CTAB of 4mL water/ethanol, protecting
Holding temperature at 100 DEG C, reflux 10min, and reaction is dried with deionized water/washing with alcohol product, 50 DEG C after terminating；
(2) tripolycyanamide is placed in the crucible added a cover, in Muffle furnace, is warming up to 550 with the programming rate of 2.3 DEG C/min
DEG C, keeping 4h, after natural cooling, the yellow powder of gained is block g-C3N4；
(3) by step (1), HW and g-C of (2) gained3N4It is scattered in respectively in 50mL methanol, ultrasonic 1h, suspension is mixed
Close and ultrasonic be placed in fume hood volatilization 2h, after methanol solution volatilization is dry, i.e. obtain by HW and g-C3N4The photocatalysis being composited
Agent.
Preferably, the mass fraction of described HW is 8wt%, described g-C3N4Mass fraction be 92wt%.
To sample 8wt%HW/g-C3N4Carry out XRD, FTIR, SEM, TEM and UV-DRS test respectively.Fig. 1 is HW, g-
C3N4And HW/g-C3N4The XRD spectra of composite catalyst, 7.6 ° of diffraction maximums are attributed to W in HW10O32 4-Characteristic diffraction peak,
The diffraction maximum of 12.8 ° and 27.6 ° is attributed to g-C3N4The characteristic diffraction peak of (100) and (002) crystal face, can see through compound
Arrive, 8wt%HW/g-C3N4Occur in that the characteristic diffraction peak of two kinds of thing phases, show that HW is compound to g-C3N4Surface.Fig. 2 is 8wt%
HW/g-C3N4Photocatalyst FTIR spectrogram.HW 2922,2854 and 1470cm-1Absworption peak be-CH in CTAB2Stretching of-chain
Vibration peak, 959 and 883,804cm-1For W=OtAnd W-ObThe stretching vibration absworption peak of-W, HW and g-C3N4After Fu He, except g-
C3N4Absworption peak, we simultaneously observe the characteristic absorption peak of HW, and this demonstrates HW and g-C3N4Compound.Fig. 3 c, 3d are
HW/g-C3N4Photocatalyst SEM photograph.Visible, HW and g-C3N4Combine closely, form the HW/g-C of good contact3N4Hetero-junctions
Structure, this point is confirmed (Fig. 4 c, 4d) at TEM photo.Fig. 5 is HW/g-C3N4The UV-DRS spectrogram of heterogeneous photocatalyst, it is seen then that
After compound, ABSORPTION EDGE is between g-C3N4And between HW.
To prepared 8wt%HW/g-C3N4Photocatalyst carries out photocatalytic activity experiment, and light source is 300W xenon lamp, uses
420nm optical filter is to ensure that incident illumination is as visible ray (λ > 420nm).The suspension of catalyst in solution is maintained by magnetic agitation
State.In experiment, 50mg catalyst is added to 50mL 10mg L-1In MO dye solution, lucifuge stirring 1h, question response thing is being urged
After adsorption-desorption balance is set up on the surface of agent, open light source and carry out light-catalyzed reaction, pipette 3.0mL the most at regular intervals
Reactant liquor, after being performing centrifugal separation on, takes the supernatant and uses Varian Cary 50UV-vis spectrophotometer to carry out quantitative analysis.
Result as shown in Figure 6, without compound g-C3N4Degradation rate be 61.4%, and 8wt%HW/g-C3N4Photocatalyst for degrading
Rate is 90.6%, and result display composite catalyst can be effectively improved Photocatalytic activity.
Embodiment 2 preparation is 5wt%HW/g-C containing HW mass fraction3N4Photocatalyst.
Carry out as steps described below:
(1) in 250mL round-bottomed flask, 0.01mol (3.3g) Na it is sequentially added into2WO4·2H2O and 4mL H2O, boils
5min, adds 6.9mL 3M HCl, is being stirred continuously lower addition and is dissolved in 0.003mol (1.46g) CTAB of 4mL water/ethanol, protecting
Holding temperature at 100 DEG C, reflux 10min, and reaction is dried with deionized water/washing with alcohol product, 50 DEG C after terminating；
(2) tripolycyanamide is placed in the crucible added a cover, in Muffle furnace, is warming up to 550 with the programming rate of 2.3 DEG C/min
DEG C, keeping 4h, after natural cooling, the yellow powder of gained is block g-C3N4；
(3) by step (1), the g-C of HW and 0.95g of the 0.05g of (2) gained3N4It is scattered in respectively in 50mL methanol, super
Sound 1h, suspension is mixed ultrasonic be placed in fume hood volatilization 2h.After methanol solution volatilization is dry, i.e. obtain by HW and g-C3N4Multiple
The photocatalyst closed.This sample is designated as 5wt%HW/g-C3N4。
To sample 5wt%HW/g-C3N4Carry out XRD test (Fig. 1).Owing to can not find HW's on the relatively low XRD of HW content
Characteristic diffraction peak, shows that HW high dispersive is present in complex.Fig. 5 is HW/g-C3N4The UV-DRS spectrum of heterojunction photocatalyst
Figure, it is seen then that 5wt%HW/g-C3N4ABSORPTION EDGE is between g-C3N4And between HW.
According to the method for embodiment 1, the catalyst material of preparation being carried out visible light catalysis activity test, result shows, can
After seeing that light irradiates 180min, the degradation rate of MO is 75.7%.
Embodiment 3 preparation is the HW/g-C of 20wt% containing HW mass fraction3N4Composite photo-catalyst.
Carry out as steps described below:
(1) in 250mL round-bottomed flask, 0.01mol (3.3g) Na it is sequentially added into2WO4·2H2O and 4mL H2O, boils
5min, adds 6.9mL 3M HCl, is being stirred continuously lower addition and is dissolved in 0.003mol (1.46g) CTAB of 4mL water/ethanol, protecting
Holding temperature at 100 DEG C, reflux 10min, and reaction is dried with deionized water/washing with alcohol product, 50 DEG C after terminating；
(2) tripolycyanamide is placed in the crucible added a cover, in Muffle furnace, is warming up to 550 with the programming rate of 2.3 DEG C/min
DEG C, keeping 4h, after natural cooling, the yellow powder of gained is block g-C3N4；
(3) by step (1), the g-C of HW and 0.80g of the 0.20g of (2) gained3N4It is scattered in respectively in 50mL methanol, super
Sound 1h, suspension is mixed ultrasonic be placed in fume hood volatilization 2h.After methanol solution volatilization is dry, i.e. obtain by HW and g-C3N4Multiple
The photocatalyst closed.This sample is designated as 20wt%HW/g-C3N4。
To sample 20wt%HW/g-C3N4Carry out XRD test (Fig. 1).20wt%HW/g-C3N47.6 °, 12.8 ° and
27.6 ° occur HW and g-C respectively3N4The characteristic diffraction peak of thing phase, shows HW and g-C3N4Form composite catalyst.Fig. 2 is
20wt%HW/g-C3N4Photocatalyst FTIR spectrogram.With 8wt%HW/g-C3N4Compare, 20wt%HW/g-C3N4HW in catalyst
2922 and 2854cm-1Belong to-CH2The stretching vibration peak intensity of-chain is relatively big, shows HW and g-C3N4Formed compound.Fig. 5 is
HW/g-C3N4The UV-DRS spectrogram of heterojunction structure photocatalyst, it is seen then that after compound, ABSORPTION EDGE is between g-C3N4And between HW.
According to the method for embodiment 1, the catalyst material of preparation being carried out visible light catalysis activity test, result shows, can
After seeing that light irradiates 180min, the degradation rate of MO is 85.5%.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.The technology of the industry
Personnel, it should be appreciated that the present invention is not restricted to the described embodiments, simply illustrating this described in above-described embodiment and description
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these become
Change and improvement both falls within scope of the claimed invention.Claimed scope by appending claims and
Equivalent defines.
Claims (3)
1. the preparation method and application of coordinated compound/carbonitride composite photo-catalyst, it is characterised in that: by ten poly-wolframic acids
Salt and g-C3N4Composition, the mass fraction of described coordinated compound is 5wt%～20wt%, described g-C3N4Mass fraction be
80wt%～95wt%, its concrete preparation method comprises the following steps:
(1) in 250mL round-bottomed flask, 0.01mol Na it is sequentially added into2WO4·2H2O and 4mLH2O, boils 5min, adds 6.9mL
3M HCl, is being stirred continuously lower addition and is being dissolved in the 0.003mol cetyl trimethylammonium bromide of 4mL water/ethanol, keeping temperature
At 100 DEG C, reflux 10min, and reaction is drying to obtain modified ten poly-wolframic acids with deionized water/washing with alcohol product, 50 DEG C after terminating
Salt；
(2) tripolycyanamide is placed in the crucible added a cover, in Muffle furnace, is warming up to 550 DEG C with the programming rate of 2.3 DEG C/min, protect
Holding 4h, after natural cooling, the yellow powder of gained is block g-C3N4；
(3) by step (1), the coordinated compound of (2) gained and g-C3N4It is scattered in respectively in 50mL methanol, ultrasonic 1h, will suspend
Liquid mixing is ultrasonic is placed in fume hood volatilization 2h, after methanol solution volatilization is dry, i.e. obtains by coordinated compound and g-C3N4Compound and
The photocatalyst become.
The preparation method and application of carbonitride heterojunction structure photocatalyst the most according to claim 1, it is characterised in that: institute
The mass fraction stating coordinated compound is 8wt%, described g-C3N4Mass fraction be 92wt%.
3., according to the preparation method and application of the carbonitride heterojunction structure photocatalyst described in claims 1 or 2, its feature exists
In: described HW/g-C3N4Composite photo-catalyst is used for visible light photocatalytic degradation water pollutant.
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