CN106861744A - A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures - Google Patents
A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures Download PDFInfo
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- CN106861744A CN106861744A CN201710050762.6A CN201710050762A CN106861744A CN 106861744 A CN106861744 A CN 106861744A CN 201710050762 A CN201710050762 A CN 201710050762A CN 106861744 A CN106861744 A CN 106861744A
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- titanium dioxide
- nitrogen
- quantum dot
- graphene quantum
- sulphur
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002096 quantum dot Substances 0.000 title claims abstract description 28
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 60
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 30
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002056 binary alloy Inorganic materials 0.000 abstract description 2
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910011210 Ti—O—N Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- 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
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Toxicology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses the one-step method for synthesizing that a kind of nitrogen sulphur is co-doped with titanium dioxide/graphene quantum dot heterostructures.Preparation method of the present invention not only can be with the codoping modified binary system of one-step synthesis, moreover, it is also possible to by nitrogen, sulphur codope titanium dioxide and nitrogen, sulphur codope graphene quantum dot makes it closely be combined with each other by stronger chemical bond.Present invention is mainly applied to photocatalytic degradation field, using degradation of methylene blue under visible ray, the photocatalysis performance of the composite is detected by degradation curve.The composite is increased substantially due to excellent visible light catalysis activity, photocatalysis efficiency compared to single titanium dioxide, and environment-friendly, will not introduce heavy metal ion, will not cause secondary pollution to the water resource for treating, and possess excellent cyclical stability.
Description
Technical field
The invention belongs to technical field prepared by nano material, and in particular to a kind of one-step synthesis nitrogen sulphur codope titanium dioxide
The preparation method of titanium/nitrogen sulphur codope graphene quantum dot composite and its photocatalytic degradation application.
Technical background
Along with industrialized development, environmental problem turns into the key factor of restriction economic development.Especially for water pollution
Problem is even more the life of influence people.Due to a large amount of discharges of organic dyestuff in industry, the water pollution problems of sternness is caused.And
And, the species of dyestuff is various, and contaminative is strong, it is difficult to degradable.Therefore, it is badly in need of one kind to have a wide range of application, raw material is cheap, source
Extensively, the catalyst of non-secondary pollution.Titanium dioxide has benefited from its strong oxidizing property, cheap nontoxic, most wide as commercial Application
Catalyst.But, titanium dioxide forbidden band is (3.2eV) wider, causes it to absorb ultraviolet light, and electronics and hole-recombination efficiency
Height, constrains its further development and practical application.
Graphene quantum dot had both had the excellent electronic transport property of Graphene, and the performance with semiconductor as a kind of
Brand-new material, it is compound with titanium dioxide to widen its light absorption range to a certain extent.But, cumbersome preparation and it was combined
Journey needs to expend more energy.How to realize that a step is modified, and successfully prepare key of the composite as problem.
The purpose of the present invention is directed to the deficiencies in the prior art, there is provided a kind of one-step synthesis nitrogen, sulphur codope titanium dioxide,
Nitrogen, the preparation method of sulphur codope graphene quantum dot composite.And it is applied to photocatalytic degradation of dye field.The composite wood
Material have synthesis cycle is short, codoping modified, catalysis activity is high, good stability the features such as.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of nitrogen sulphur be co-doped with titanium dioxide/
The one-step method for synthesizing of graphene quantum dot hetero-junctions, makes it to be degraded to dyestuff under visible light, and will not make
Into secondary pollution.
The purpose of the present invention is achieved through the following technical solutions：
A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures, and its step has：
(1) by citric acid and thiocarbamide according to mol ratio 2:1~1:3 are dissolved in dimethylformamide, the concentration of citric acid
It is 12.5mol/L.
(2) during titanium dioxide (P25) adds the solution that step 1 is obtained, stirring obtains suspension, and the concentration of titanium dioxide is
15.6mol/L。
(3) suspension that step 2 is obtained is moved into reactor, and is reacted 6 hours at 180 DEG C, be centrifugally separating to obtain ash
Color product.
(4) gray product for obtaining will be reacted in step 3 respectively with after cleaning, vacuum drying finally gives nitrogen-sulphur and is co-doped with
Miscellaneous titanium dioxide/nitrogen-sulphur codope graphene quantum dot composite.
Further, in step 1 citric acid and the optimum molar ratio of thiocarbamide is 1:1.
Further, step 3 centrifugation, in 8000-9000rpm, the time was at 20-30 minutes for rotating speed.
Further, in the step 4, cleaned with ethanol and ultra-pure water respectively, each to clean twice, centrifugation, rotating speed
In 8000-9000rpm, centrifugation time was at 10-20 minutes.
The beneficial effects of the invention are as follows：The present invention has obtained nitrogen, sulphur codope dioxy by simple step solvent-thermal method
Change titanium, nitrogen, sulphur codope graphene quantum dot composite, material can apply to photocatalysis field.In traditional experiment
In the preparation process of room, at least need three one-step hydrothermals just to prepare the composite, save nearly 48 hours of time.However, I
Using a step solvent heat scheme, not only synthesized nitrogen-sulphur codope titanium dioxide and nitrogen-sulphur codope Graphene quantum
Point, and both form hetero-junctions, are more beneficial for the raising of catalytic performance..In terms of pattern, by solvent heat effect, meeting
Titanium dioxide (101) crystal face is more exposed, and titanium dioxide (101) active highest, catalytic process can be accelerated
Carrying out.In terms of band gap, the hetero-junctions formed by codope, energy gap is substantially reduced, and is dropped compared to pure phase titanium dioxide
Low 0.6eV, can absorb the visible ray of 500nm or so.In terms of catalysis, nitrogen sulphur codope hetero-junctions shows excellent catalytic
Can, most degradation efficiency can reach more than 90% within 120 minutes, hence it is evident that better than the titanium dioxide and dioxy of single nitrogen sulfur doping
Change titanium-graphene quantum dot compound.In terms of cyclical stability, nitrogen sulphur codope hetero-junctions, material has good stabilization
Property, by 4 circulation experiments, degradation efficiency loss control is 2.57%, and the proportion of goods damageds than conventional 10% are much smaller, Ke Yishi
Conjunction is recycled for multiple times.Summary, the synthetic method cost of material is low, and step is simple, and superior performance, stability is high, suitable large quantities of
Amount production.
Brief description of the drawings
Fig. 1 is nitrogen prepared by the embodiment of the present invention 1~3, sulphur codope titanium dioxide, nitrogen, sulphur codope Graphene quantum
The X-ray diffractogram (XRD) of point composite.
Fig. 2 is nitrogen prepared by the embodiment of the present invention 2, and sulphur codope titanium dioxide, nitrogen, sulphur codope graphene quantum dot is answered
The scanning electron microscope diagram (SEM) of condensation material.
Fig. 3 is nitrogen prepared by the embodiment of the present invention 2, and sulphur codope titanium dioxide, nitrogen, sulphur codope graphene quantum dot is answered
The transmission electron microscope figure (TEM) of condensation material.
Fig. 4 is nitrogen prepared by the embodiment of the present invention 2, and sulphur codope titanium dioxide, nitrogen, sulphur codope graphene quantum dot is answered
The x-ray photoelectron energy spectrum diagram (XPS) of condensation material.
Fig. 5 is nitrogen prepared by the embodiment of the present invention 1~3, sulphur codope titanium dioxide, nitrogen, sulphur codope Graphene quantum
The unrestrained launching light spectrogram (UV-bis) of UV, visible light of point composite.
Fig. 6 is nitrogen prepared by the embodiment of the present invention 1~3, sulphur codope titanium dioxide, nitrogen, sulphur codope Graphene quantum
The catalytic degradation dyestuff figure of the visible ray of point composite.
Fig. 7 is nitrogen prepared by the embodiment of the present invention 2, and sulphur codope titanium dioxide, nitrogen, sulphur codope graphene quantum dot is answered
The catalytic degradation dyestuff cycle efficieny figure of the visible ray of condensation material.
More than in each figure, A is commercially available titania powder (P25), and B prepares nitrogen, sulphur codope dioxy for embodiment 1
Change titanium, nitrogen, sulphur codope graphene quantum dot composite NSTG (2:1), C is NSTG (1 prepared by embodiment 2:1) composite wood
Material, D is that embodiment 3 prepares NSTG (1:3) composite.
Specific embodiment
Embodiment 1：
Prepare nitrogen, sulphur codope titanium dioxide, nitrogen, sulphur codope graphene quantum dot composite NSTG (2:1)
(1) it is 2 according to the mol ratio of citric acid and thiocarbamide:1 ratio, weighs the citric acid of 0.42g and the sulphur of 0.08g
Urea.
(2) powder that step 1 is weighed is added sequentially in the dimethyl formamide solution of 8ml, quick stirring is complete to its
CL.
(3) 100mg titanium dioxide (P25) powder is weighed, is slowly added in the solution that step 2 is obtained, quick stirring is to outstanding
Turbid liquid.
(4) suspension that step 3 is obtained is moved to the reactor of 40ml, and is reacted 6 hours at 180 DEG C.
(5) room temperature is naturally cooled to, reactor is removed, 8500rpm will be precipitated 20 minutes, centrifugation obtains grey tinctorial pattern
Product.
(6) sample for obtaining step 5 is first cleaned 2 times with ethanol, 8500rpm 10 minutes, outwells supernatant, obtains sample
Product.
(7) sample for being obtained with ultra-pure water cleaning step 6 again 2 times, 8500rpm 10 minutes outwells supernatant, obtains sample
Product.
(8) sample for obtaining step 7 is vacuum dried 12 hours at 60 DEG C, obtains nitrogen, sulphur codope titanium dioxide,
Nitrogen, sulphur codope graphene quantum dot composite.
(9) methylene blue of 80ml is measured, concentration 10mg/L weighs the sample 20mg prepared in step 8, is added to
State in solution, under 100W, be placed in beaker in magnetic stirring apparatus and stir by ultrasonic disperse 30 minutes, and 30 points are stirred in camera bellows
Clock, makes 300W xenon lamps be irradiated sample, is placed in 10ml centrifuge tubes every 1 small taking-up 4ml solution, 5000rpm 5 minutes
Centrifugation, separates out catalyst, removes supernatant to 5ml centrifuge tubes, to be measured.After radiating 4 hours at visible wavelengths, use
The blue concentration of UV-bis measurement centrifuge tube methylenes.The photocatalytic degradation of dye performance for measuring is as shown in Figure 6.
(10) in recycling step 9 light-catalyzed reaction remaining sample, washing and drying, continuation operated according to step 9, follow successively
Ring 3 times, the photocatalytic degradation efficiency change for measuring is as shown in Figure 7.
Embodiment 2：
In embodiment 1, will be changed in step 1：Mol ratio according to citric acid and thiocarbamide is 1:1 ratio, weighs
The citric acid of 0.42g and the thiocarbamide of 0.15g.Remaining step is consistent with embodiment 1.Sample NSTG (1 is finally obtained:1).Light
The step of catalytic degradation dyestuff performance test process is with embodiment 19 is identical.
Fig. 3 is the TEM figures that embodiment 2 prepares sample, under low power, it can be seen that the titanium dioxide of nitrogen sulfur doping is with nanometer
Granule-morphology is present, and nitrogen sulfur doping graphene quantum dot is firmly attached to titanium dioxide surface, shape due to small-sized (about 5nm)
Into hetero-junctions.Under high-resolution, it may be clearly seen that exposed (101) crystal face of titanium dioxide, due to the effect of hetero-junctions, tightly
Close connection is nitrogen sulfur doping graphene quantum dot (1120) crystal face, and the two crystal face synergy can accelerate catalytic process
Carrying out, making the sample of preparation has excellent catalytic performance.
Fig. 7 is the cyclical stability analysis chart that embodiment 2 prepares sample, it can be seen that nitrogen sulfur doping titanium dioxide, nitrogen sulphur
After 4 times circulate degradation experiment, degradation efficiency is lost 2.57% doped graphene quantum dot heterostructures.Conventional is single
The degradation efficiency of doping type titanium dioxide or titanium dioxide-graphene quantum dot compound is lost 10% or so.Embodiment 2
The sample of preparation has very good cyclical stability, and this is also to have benefited under hetero-junctions effect, stronger between the two
Chemical bonding is acted on.
Embodiment 3:
In embodiment 1, will be changed in step 1：Mol ratio according to citric acid and thiocarbamide is 1:3 ratio, weighs
The citric acid of 0.42g and the thiocarbamide of 0.46g.Remaining step is consistent with embodiment 1.Sample NSTG (1 is finally obtained:3).Light
The step of catalytic degradation dyestuff performance test process is with embodiment 19 is identical.
Fig. 4 is the N 1s and S 2p high-resolution sign that embodiment 2 prepares sample, under N 1s high-resolution, 399.2,
399.7,400.3,401.3eV correspond to C-N-C respectively, and O-Ti-N, N-H, Ti-O-N is bonded, under S 2p high-resolution,
163.6,164.7,168.3,169.6eV correspond to S 2p respectively3/2, S 2p1/2, S=O, S-O bonding, side proves, embodiment
3 samples for preparing are nitrogen sulfur doping titanium dioxide, the hetero-junctions of nitrogen sulfur doping graphene quantum dot, also, have between hetero-junctions
Very strong chemical bond, is conducive to being lifted the stability of material.
Fig. 5 is the UV-vis DRS of embodiment 1 (B), embodiment 2 (C) and (D) product of embodiment 3 and P25 (A)
Spectrogram, from energy gap as can be seen that the B of the preparation of embodiment 1,2,3, the energy gap of C, D is respectively than single titanium dioxide
Titanium reduces 0.37,0.60,0.48eV, and this is conducive to electron-hole preferably to separate, and lifts Photocatalytic Degradation Property.
Fig. 6 is embodiment 1, B prepared by example 2 and example 3, the degradation curve of C, D and P25, it can be seen that implement 2 preparations
Sample C performances are optimal, can just reach 90% degradation efficiency within 120 minutes.Simple nitrogen sulfur doping titanium dioxide and titanium dioxide
The degradation efficiency for commonly reaching 50-60% or so for 120 minutes of titanium-graphene quantum dot compound, sample prepared by embodiment 2
Photocatalysis performance be substantially better than them, have very excellent Photocatalytic Degradation Property.
Illustrated by above example, composite material and preparation method thereof of the present invention has simple to operate, with low cost, ring
The advantages of border close friend, repeatability height, non-secondary pollution, and nitrogen can be obtained by the method for a step solvent heat, sulphur is co-doped with
Miscellaneous modified binary system.The nitrogen prepared from the curve D of accompanying drawing 6, the present invention, sulphur codope titanium dioxide, nitrogen, sulphur is co-doped with
Miscellaneous graphene quantum dot composite, tests through photocatalytic degradation of dye, after camera bellows is adsorbed 30 minutes, degrades 4 hours, can be with
Degraded is complete, the performance (the curve A of Fig. 6) of the performance far above traditional titanium dioxide (P25) of its photocatalytic degradation of dye, says
Sample prepared by the bright present invention has catalysis activity very high.Final resulting solution is nontoxic, the row after suitable industrial wastewater cleaning
Put, reduce the excessive consumption of the energy.
Claims (4)
1. a kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures, it is characterised in that including with
Lower step：
(1) by citric acid and thiocarbamide according to mol ratio 2:1~1:3 are dissolved in dimethylformamide, and the concentration of citric acid is
12.5mol/L。
(2) during titanium dioxide (P25) adds the solution that step 1 is obtained, stirring obtains suspension, and the concentration of titanium dioxide is
15.6mol/L。
(3) suspension that step 2 is obtained is moved into reactor, and is reacted 6 hours at 180 DEG C, be centrifugally separating to obtain grey product
Thing.
(4) gray product for obtaining will be reacted in step 3 respectively with after cleaning, vacuum drying finally gives nitrogen-sulphur codope two
Titanium oxide/nitrogen-sulphur codope graphene quantum dot composite.
2. method according to claim 1, it is characterised in that the optimum molar ratio of citric acid and thiocarbamide in step 1
It is 1:1.
3. method according to claim 1, it is characterised in that step 3 centrifugation, rotating speed in 8000-9000rpm, when
Between at 20-30 minutes.
4. method according to claim 1, it is characterised in that in the step 4, cleaned with ethanol and ultra-pure water respectively,
It is each to clean twice, centrifugation, in 8000-9000rpm, centrifugation time was at 10-20 minutes for rotating speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710050762.6A CN106861744B (en) | 2017-01-23 | 2017-01-23 | A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710050762.6A CN106861744B (en) | 2017-01-23 | 2017-01-23 | A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures |
Publications (2)
| Publication Number | Publication Date |
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| CN106861744A true CN106861744A (en) | 2017-06-20 |
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| CN107376974A (en) * | 2017-08-16 | 2017-11-24 | 江苏海普功能材料有限公司 | A kind of high-performance nonmetal doping Ti based photocatalysts and preparation method thereof |
| CN107983386A (en) * | 2017-12-01 | 2018-05-04 | 江苏理工学院 | A kind of ultra-thin BiOCl/ nitrogen-doped graphenes quantum dot composite photo-catalyst and preparation method |
| CN108906107A (en) * | 2018-07-06 | 2018-11-30 | 广东海洋大学 | A kind of preparation method of sulfur and nitrogen co-doped titanium dioxide |
| CN108906032A (en) * | 2018-07-05 | 2018-11-30 | 山东理工大学 | A kind of GOQDS/TiO2/WO3The preparation and its application of photochemical catalyst |
| CN109626364A (en) * | 2019-01-29 | 2019-04-16 | 东北大学 | A kind of preparation method of nitrogen sulphur codope three-dimensional grapheme |
| CN110016731A (en) * | 2019-04-30 | 2019-07-16 | 张慧 | A kind of quantum titanium fibrous material |
| CN110061252A (en) * | 2019-05-08 | 2019-07-26 | 安康学院 | A kind of fuel battery negative pole oxygen reduction catalyst nitrogen sulphur codope graphene/carbon point composite material and preparation method and application |
| CN110124636A (en) * | 2019-05-29 | 2019-08-16 | 张慧 | A kind of magnetic Nano fibrous material for textile waste processing |
| CN110813360A (en) * | 2019-11-28 | 2020-02-21 | 吉林大学 | Nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst and preparation method and application thereof |
| CN111573653A (en) * | 2020-05-19 | 2020-08-25 | 山西大学 | Nitrogen-sulfur self-doped fluorescent carbon quantum dot and preparation method and application thereof |
| CN113690432A (en) * | 2021-08-13 | 2021-11-23 | 肇庆中特能科技投资有限公司 | Graphene quantum dot/PbOx composite material and preparation method and application thereof |
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| CN107983386B (en) * | 2017-12-01 | 2020-12-08 | 江苏理工学院 | Ultrathin BiOCl/nitrogen-doped graphene quantum dot composite photocatalyst and preparation method thereof |
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| CN110016731A (en) * | 2019-04-30 | 2019-07-16 | 张慧 | A kind of quantum titanium fibrous material |
| CN110061252A (en) * | 2019-05-08 | 2019-07-26 | 安康学院 | A kind of fuel battery negative pole oxygen reduction catalyst nitrogen sulphur codope graphene/carbon point composite material and preparation method and application |
| CN110124636A (en) * | 2019-05-29 | 2019-08-16 | 张慧 | A kind of magnetic Nano fibrous material for textile waste processing |
| CN110124636B (en) * | 2019-05-29 | 2022-07-26 | 太仓市洪宇新材料科技有限公司 | Magnetic nanofiber material for textile industry wastewater treatment |
| CN110813360A (en) * | 2019-11-28 | 2020-02-21 | 吉林大学 | Nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst and preparation method and application thereof |
| CN111573653A (en) * | 2020-05-19 | 2020-08-25 | 山西大学 | Nitrogen-sulfur self-doped fluorescent carbon quantum dot and preparation method and application thereof |
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