CN108889329A - A kind of quantum-dot modified multi-stage porous TiO2-SiO2 photochemical catalyst of carbonitride - Google Patents
A kind of quantum-dot modified multi-stage porous TiO2-SiO2 photochemical catalyst of carbonitride Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000002096 quantum dot Substances 0.000 title claims abstract description 26
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 title abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 26
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004038 photonic crystal Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
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- 150000001875 compounds Chemical class 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
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- 239000007787 solid Substances 0.000 claims description 4
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 15
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- 239000002351 wastewater Substances 0.000 abstract description 11
- 230000003115 biocidal effect Effects 0.000 abstract description 9
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 abstract description 9
- 229960004306 sulfadiazine Drugs 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- -1 isopropyl Ester Chemical class 0.000 description 3
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- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 230000001360 synchronised effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
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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
- C02F2101/40—Organic compounds containing sulfur
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Physical Water Treatments (AREA)
Abstract
The present invention relates to a kind of quantum-dot modified hierarchical porous structure TiO of carbonitride2‑SiO2Photochemical catalyst and preparation method thereof.The method is mainly characterized in that by the method that loads in situ in synthesizing ordered multi-stage porous TiO2‑SiO2During material, introduces nitridation carbon quantum dot and obtain the quantum-dot modified hierarchical porous structure TiO of carbonitride after calcination method removes template2‑SiO2Photochemical catalyst.Compared with prior art, the method that the present invention uses is simple and easy to operate, and efficiently using raw material and nitridation carbon quantum dot can be made to be supported in the hole wall of multistage pore titanium oxide silica, promote the raising of photocatalytic activity, hierarchical porous structure orderly simultaneously also provides the channel of good guest molecule diffusion and transmission, and the organic pollutants such as the photochemical catalyst Pyrogentisinic Acid, the sulphadiazine that are prepared and practical high concentration antibiotic waste water is made to have preferable catalytic degradation activity.
Description
Technical field
The present invention relates to nano-photocatalyst material fields, are aoxidized by way of loading in situ in hierarchical porous structure titanium oxide
Load nitridation carbon quantum dot, proposes a kind of novel photocatalyst and preparation method thereof in silicon hole wall.
Background technique
Mesopore silicon oxide is a kind of novel nano-material developed in recent years, it has the ratio table of up to 1000m2/g
The duct of area, continuously adjustable aperture and height long-range order, higher thermal stability etc..These excellent structural behaviours
So that they are being catalyzed, drug loading, exhaust gas absorption, separating-purifying and solar energy photoelectric conversion etc. have huge answer
With value, the extensive concern of each related fields has just been obtained once report.Especially in recent years, continuous with synthetic technology
Innovation, various structures such as KIT, MSU and SBA mesopore silicon oxide are constantly seen in report, and the research of mesoporous material shows flourishing hair
The scene of exhibition, the research in relation to their synthetic method, synthesis mechanism and application etc. have been achieved for great successes.
Photonic crystal (PC) with ordered big hole structure becomes research hotspot in recent years.Periodically " opal " mould
The self assembly of plate can refer to lead the infiltration and deposition of persursor material, with generation " counter opal " (inverse opals, IOs) light
Sub- crystal structure.The slow light effect of inverse opal photonic crystal and more light scattering effects can extend optical path, increase the absorption of light,
To improve the photocatalytic activity of material.Photon crystal structure is prepared to the silica material of multi-stage porous in conjunction with meso-hole structure
Material, the material have both the structural advantage of meso pore silicon oxide material high-specific surface area, high thermal stability and photon crystal material.So
And since silica itself does not have catalytic activity, multi-stage porous silica material is limited in photocatalytic pollutant degradation
Using.Titanium oxide is introduced into multi-stage porous silica material, hierarchical porous structure TiO2-SiO2 photonic crystal photochemical catalyst is obtained,
The structural advantage that the material has both multi-stage porous simultaneously has photocatalytic activity again, being capable of effective degradation of contaminant.But titanium oxide
Forbidden bandwidth be 3.2eV, the absorption of corresponding ultraviolet light, it is seen that photolytic activity is insufficient.
Graphite phase carbon nitride (g-C3N4), forbidden bandwidth 2.7eV are that a kind of excellent have chemical stability nonmetallic
Semiconductor is widely used in organic pollutant degradation.In recent years, graphite phase carbon nitride quantum dot (CNQDs) has very strong
Blue emission and upper conversion behavior receive significant attention.In conjunction in CNQDs and hierarchical porous structure oxidation silicon oxide
TiO2 forms Z framework, improves material specific surface area, utilization rate and charge transfer effciency to visible light, is advantageously implemented light
Effective degradation of the catalyst to organic pollutant.
Report based on nitridation carbon quantum dot design photochemical catalyst is also seldom, by nitridation carbon quantum dot and multilevel hole material knot
The report that conjunction prepares high efficiency photocatalyst does not have substantially yet.Based on background above, it is more that the present invention is supported on nitridation carbon quantum dot
In the hole wall of grade pore titanium oxide silica, promote the raising of photocatalytic activity, while orderly hierarchical porous structure also provides very
The channel of good guest molecule diffusion and transmission, makes the organic pollutants such as the photochemical catalyst Pyrogentisinic Acid, the sulphadiazine that are prepared
And practical antibiotic waste water has preferable catalytic degradation activity.
Summary of the invention
The present invention prepares the quantum-dot modified hierarchical porous structure TiO2- of carbonitride using the method loaded in situ, one-step method
SiO2 photochemical catalyst.During preparing the composite photo-catalyst, addition acetylacetone,2,4-pentanedione is alleviated as titanium source hydrolysis inhibitor
The too fast hydrolysis of titanium source, while adding silicon source (tetrabutyl silicate), the nitridation carbon quantum dot prepared and titanium source (metatitanic acid isopropyl
Ester), it is fed into polystyrene sphere template, using three in acid system, the micella of nonionic surfactant formation
Upper synchronous hydrolysis, easy synthesizes catalyst.Removing template is removed using high-temperature calcination, obtains the quantum-dot modified multi-stage porous of carbonitride
Structure Ti O2-SiO2 photochemical catalyst has the organic pollutants such as sulphadiazine, phenol and practical antibiotic waste water preferable
Photocatalytic degradation effect.
The present invention is to prepare above-mentioned photochemical catalyst, and used processing step is as follows：
Carbonitride quantum dot solution is prepared using sodium citrate and urea as raw material by solid phase hydro-thermal method；Pore creating material is molten
Solution is vigorously stirred certain time in ethanol solution, then reduces mixing speed, and tetrabutyl silicate, hydrochloric acid, levulinic is added
Ketone, carbonitride quantum dot solution, obtains mixed solution at isopropyl titanate, and stirring is fed into polystyrene moulding, certain
Dry certain time is hydrolyzed under temperature and humidity, is then removed removing template in certain temperature calcining certain time in air, is obtained
The quantum-dot modified hierarchical porous structure TiO2-SiO2 photonic crystal photochemical catalyst of carbonitride.
The reaction system is acid solution, promotes the hydrolysis speed that isopropyl titanate is controlled while teos hydrolysis
Degree avoids the too fast hydrolysis of isopropyl titanate that titanium is caused to be unable to monodisperse in mesoporous framework；
The concentration of hydrochloric acid solution is 2mol/L -6mol/L；The pore creating material includes F127, P123 etc.；Described
Mixing time is 0.5-2h；The hydrolysis temperature is 30 DEG C -60 DEG C, humidity 40-60%；The calcination temperature is 400-
600℃；The calcination time is 2h-6h.
Advantage of the invention is embodied in：
1) method of the invention hydrolyzes drying under certain temperature and humidity by pore creating material and template, common to make
With the hierarchical porous structure simultaneously with orderly mesopore orbit and counter opal structure, so that titanium oxide and dialysis obtained
It is compound in the skeleton of multi-stage porous to nitrogenize carbon quantum dot, three generates synergistic effect, improves photocatalytic activity；
2) introducing synchronous with titanium of nitridation carbon quantum dot can make the two that can interact codope in multi-stage porous oxidation
In the hole wall of silicon, and it ensure that orderly smooth duct and higher specific surface area；
3) orderly mesopore orbit and counter opal structure provide the channel of good guest molecule diffusion and transmission,
Be conducive to the raising of photocatalytic activity；
4) the quantum-dot modified hierarchical porous structure TiO2-SiO2 photochemical catalyst of the carbonitride being prepared is to sulphadiazine, benzene
The organic pollutants such as phenol and the practical antibiotic waste water of high concentration have preferable catalytic degradation activity；
5) nitridation carbon quantum dot and hierarchical porous structure generate synergistic effect, promote the raising of photocatalytic activity；
6) relative to the method for modifying such as traditional doping, compound, in-situ synthesis equipment is simple, and it is convenient to operate, and can be high
Effect utilizes raw material, greatly reduces production cost, is conducive to industrialization promotion.
Detailed description of the invention
Fig. 1 (a) Me-TSCN-IO, (b) Me-TS-IO, (c) Me-TSCN, (d) Me-TS, (e) TSCN-IO, (f) TS-
IO, (g) bulk-TSCN, (h) SEM photograph of bulk-TS.
Fig. 2 (a) Me-TSCN-IO, (b) Me-TS-IO, (c) Me-TSCN, (d) Me-TS, (e) TSCN-IO, (f) TS-
IO, (g) bulk-TSCN, (h) the TEM photo of bulk-TS.
The HRTEM photo of Fig. 3 .Me-TSCN-IO.
The quantum-dot modified hierarchical porous structure TiO2-SiO2 photonic crystal photochemical catalyst (Me-TSCN-IO) of Fig. 4 carbonitride
XRD spectra.
(a) nitrogen adsorption desorption isotherm (b) pore size distribution curve of Fig. 5 sample.
The impedance diagram of Fig. 6 sample.
Fig. 7 .Me-TSCN-IO is under the 300W xenon lamp for installing AM1.5 optical filter additional to 10mg/L (a) phenol (b) sulphadiazine
Degrading activity figure.
Degrading activity figure of Fig. 8 .Me-TSCN-IO to practical antibiotic waste water.
Cyclical stability figure of Fig. 9 sample Me-TSCN-IO to (a) phenol (b) sulphadiazine photocatalytic degradation.
Specific embodiment
The present invention will be described in more detail below by specific embodiment, but protection scope of the present invention not by
It is limited to these embodiments.
Nitrogenize the preparation of carbon quantum dot (CNQDs)：
Using urea and sodium citrate as presoma, using low-temperature solid hydro-thermal method, water is prepared after dialysis treatment
Phase carbon nitride quantum dot.Specifically, by 0.081g sodium citrate and 0.101g urea ground and mixed it is uniform after be transferred to polytetrafluoro
In ethylene reaction kettle liner.Stainless steel outer sleeve screwing hermetic is good, 2h is kept at 180 DEG C in electric heating constant-temperature blowing drying box.
Natural cooling at room temperature after autoclave is taken out, after brown solid dehydrated alcohol supersound washing three times will be obtained, is packed into
It in MWCO3500 specification bag filter, dialyses in 20mL deionized water for 24 hours at room temperature, it is water-soluble to obtain yellowish nitridation carbon quantum dot
Liquid.
Embodiment 1
Me-TSCN-IO is synthesized, nitridation carbon quantum dot, pore creating material such as P123, tetrabutyl silicate are added simultaneously in preparation process
And isopropyl titanate, and using polystyrene as template, specifically it is：
After 30mL EtOH is added in 50mL beaker, 2gP123 is added, stirring 30min is to being completely dissolved.In clear solution
Middle addition 0.89mL tetrabutyl silicate (TEOS), 1mL HCl (4mol/L), 1mL inhibitor acetylacetone,2,4-pentanedione, 4.8mL metatitanic acid isopropyl
Ester (TTIP) and 5mL CNQDs aqueous solution.After stirring 2h at room temperature, precursor solution is filled into 355nm PS template.It is permanent
Constant temperature and humidity case after humidity 55% hydrolyzes 3 days, is transferred to 70 DEG C of oven dryings 3 days, under air atmosphere in Muffle furnace with 40 DEG C of temperature
500 DEG C of calcining 4h (1 DEG C/min of heating rate) so that titanium oxide and nitridation carbon quantum dot in skeleton it is compound to get to nitridation
The modified multistage pore titanium oxide silica composite photo-catalyst of carbon quantum dot.
Comparative example 1
Me-TS-IO is synthesized, pore creating material such as P123, tetrabutyl silicate and isopropyl titanate, i.e. nitrogen is only added in preparation process
The additional amount for changing carbon quantum dot is 0, and using polystyrene as template：
After 30mL EtOH is added in 50mL beaker, 2g P123 is added, stirring 30min is to being completely dissolved.Transparent molten
0.89mL tetrabutyl silicate (TEOS), 1mL HCl, 1mL inhibitor acetylacetone,2,4-pentanedione, 4.8mL isopropyl titanate are added in liquid
(TTIP) with 5mL deionized water.After stirring 2h at room temperature, precursor solution is filled into 355nm PS template.Constant temperature and humidity
Case after humidity 55% hydrolyzes 3 days, is transferred to 70 DEG C of oven dryings 3 days, under air atmosphere 500 DEG C in Muffle furnace with 40 DEG C of temperature
4h (1 DEG C/min of heating rate) is calcined to get multistage pore titanium oxide silica composite photo-catalyst is arrived.
Comparative example 2
Synthesize Me-TSCN, be added nitridation carbon quantum dot in preparation process simultaneously, pore creating material such as P123, tetrabutyl silicate and
Isopropyl titanate, no polystyrene sphere are template：
After 30mL EtOH is added in 50mL beaker, 2g P123 is added, stirring 30min is to being completely dissolved.Transparent molten
0.89mL tetrabutyl silicate (TEOS), 1mL HCl, 1mL inhibitor acetylacetone,2,4-pentanedione, 4.8mL isopropyl titanate are added in liquid
(TTIP) it with 5mL CNQDs aqueous solution, is put into climatic chamber after stirring 2h at room temperature with 40 DEG C of temperature, humidity 55% hydrolyzes
After 3 days, be transferred to 70 DEG C of oven dryings 3 days, under air atmosphere in Muffle furnace 500 DEG C of calcining 4h (1 DEG C/min of heating rate), i.e.,
Obtain the quantum-dot modified meso-porous titanium oxide silica composite photo-catalyst of carbonitride.
Comparative example 3
TSCN-IO is synthesized, is added in preparation process and nitridation carbon quantum dot, tetrabutyl silicate and isopropyl titanate is only added,
When i.e. the additional amount of pore creating material such as P123 is 0, using polystyrene sphere as catalyst obtained by template:
After 30mL EtOH is added in 50mL beaker, 30min is to being completely dissolved for stirring.0.89mL is added in clear solution
Tetrabutyl silicate (TEOS), 1mL HCl, 1mL inhibitor acetylacetone,2,4-pentanedione, 4.8mL isopropyl titanate (TTIP) and 5mL CNQDs water
Solution.After stirring 2h at room temperature, precursor solution is filled into 355nm PS template.Climatic chamber is wet with 40 DEG C of temperature
Degree 55% hydrolysis 3 days after, be transferred to 70 DEG C of oven dryings 3 days, under air atmosphere in Muffle furnace 500 DEG C of calcining 4h (heating rates 1
DEG C/min), so that titanium oxide and nitridation carbon quantum dot in skeleton it is compound to get arrive the quantum-dot modified macroporous structure oxygen of carbonitride
Change silicon oxide composite photo-catalyst.
Comparative example 4
Bulk-TS is synthesized, is added in preparation process and tetrabutyl silicate and isopropyl titanate, i.e. pore creating material such as P123 is only added
When additional amount with nitridation carbon quantum dot is all 0, no polystyrene sphere is as catalyst obtained by template:
30mL dehydrated alcohol, 0.89mL tetrabutyl silicate (TEOS), 1mL HCl, 1mL inhibitor second are added in 50mL beaker
Acyl acetone, 4.8mL isopropyl titanate (TTIP) and 5mL deionized water are put into climatic chamber after stirring 2h at room temperature with temperature
Degree 40 DEG C, humidity 55% hydrolyze 3 days after, be transferred to 70 DEG C of oven dryings 3 days, under air atmosphere in Muffle furnace 500 DEG C of calcining 4h
(1 DEG C/min of heating rate) to get arrive block-like oxidation silicon oxide composite photo-catalyst.
Experiment and data
The active investigation method of photocatalytic degradation simulating pollution object provided by the invention is as follows：
50mg composite photo-catalyst is taken, is added in quartz glass tube, then measure 50mL 10mg/L target organic pollutant
Solution is added, and so that catalyst is adsorbed 30min in advance to organic matter under magnetic agitation, makes up to adsorption-desorption balance, samples conduct
Light degradation initial concentration.Then photocatalysis degradation organic contaminant reaction is carried out under 300W xenon lamp, is sampled at regular intervals
It is placed in centrifuge tube and is centrifuged, supernatant liquor is taken to filter out catalyst with filtering head, if target is simulation organic wastewater such as phenol, sulphur
Amic metadiazine then tests degradation amount by high performance liquid chromatography, if target is actual waste water, such as North China pharmacy group Limited Liability is public
Department's antibiotic actual waste water then passes through COD analyzer and TOC analyzer test COD (COD) and total organic carbon (TOC),
Then plot analysis.
Fig. 1 is scanning electron microscope (SEM) photo for the sample that embodiment 1 and comparative example 1-4 are obtained.From SEM photograph
It is upper to can see the quantum-dot modified hierarchical porous structure TiO2-SiO2 photonic crystal (Me-TSCN-IO) of carbonitride, hierarchical porous structure
The quantum-dot modified macroporous structure TiO2-SiO2 photonic crystal (TSCN- of TiO2-SiO2 photonic crystal (Me-TS-IO), carbonitride
IO) there is apparent counter opal macroporous structure, the quantum-dot modified meso-hole structure TiO2-SiO2 (Me-TSCN) of carbonitride and general
Logical TiO2-SiO2 (bulk-TS) does not have the macroporous structure of rule then.
Fig. 2 is transmission electron microscope (TEM) photo for the sample that embodiment 1 and comparative example 1-4 are obtained.From TEM photo
It is upper it can be seen that Me-TSCN-IO, Me-TS-IO, TSCN-IO have an apparent counter opal macroporous structure, Me-TSCN and
Bulk-TS does not have the macroporous structure of rule then.
Fig. 3 is high power transmission electron microscope (HRTEM) photo for the Me-TSCN-IO sample that embodiment 1 obtains.From
On HRTEM photo it can be seen that clearly meso-hole structure and counter opal structure, it was demonstrated that the formation of hierarchical porous structure, and can
To observe different lattice fringes, (002) crystal face of carbonitride and (101) of (100) crystal face and titanium oxide are respectively corresponded
Crystal face, it was demonstrated that the successful load of nitridation carbon quantum dot.
Fig. 4 is the XRD spectra for the sample that embodiment 1 and comparative example 1-4 are obtained.It can be observed that oxygen on wide-angle XRD spectra
Change the appearance of titanium, because the amount of carbonitride is very little without observing the appearance of carbonitride.
Fig. 5 is case study on implementation 1, the nitrogen adsorption desorption isotherm of sample prepared by comparative example 2-3 and pore-size distribution are bent
Line chart.It can be seen that Me-TSCN-IO has both large pore material TSCN-IO and mesoporous material Me- by nitrogen adsorption desorption isotherm figure
The hysteresis loop of TSCN illustrates that Me-TSCN-IO has hierarchical porous structure.It can illustrate mesoporous introducing by pore size distribution curve figure
So that Me-TSCN-IO has the Kong Rong bigger than large pore material TSCN-IO.
Fig. 6 is the impedance diagram for the sample that embodiment 1 and comparative example 1-3 are obtained.From the figure, it can be seen that nitridation carbon quantum dot
Modified multistage pore titanium oxide oxidation silicon photonic crystal has the smallest impedance radius, illustrates that the load for nitrogenizing carbon quantum dot promotes
The separation of light induced electron and hole.
Fig. 7 is that photochemical catalyst obtained by embodiment 1 and comparative example 1-4 is right under the 300W xenon lamp for installing AM1.5 optical filter additional
The degrading activity figure of 10mg/L phenol and sulphadiazine.Degradation for both phenol and sulphadiazine, nitridation carbon quantum dot change
Property multi-stage porous its catalytic activity of TiO2-SiO2 photonic crystal Me-TSCN-IO than the multi-stage porous modified without nitridation carbon quantum dot
TiO2-SiO2 photonic crystal Me-TS-IO has superior photocatalytic activity, it was demonstrated that the load of nitridation carbon quantum dot helps
In the promotion of photocatalytic activity；Also, the quantum-dot modified multi-stage porous TiO2-SiO2 photonic crystal Me-TSCN-IO ratio of carbonitride
The quantum-dot modified TiO2-SiO2 material Me-TSCN of simple meso-hole structure carbonitride, simple macroporous structure nitridation carbon quantum dot change
Property TiO2-SiO2 photonic crystal TSCN-IO and bulk TiO2-SiO2 material bulk-TS catalyst effect be good, it was demonstrated that multistage
Pore structure has more more advantageous than simple mesoporous and macroporous structure.In terms of comprehensive, carbon quantum dot and hierarchical porous structure are nitrogenized
Synergistic effect make the organic contaminations such as material light catalysis degradation of phenol and sulphadiazine activity improve.
Fig. 8 is that 1 gained photochemical catalyst of embodiment blames North China pharmacy group under the 300W xenon lamp for installing AM1.5 optical filter additional
Appoint the degrading activity figure of Co., Ltd (Hebei, Shijiazhuang) high concentration antibiotic actual waste water.It can be seen from the figure that with light
According to progress, COD the and TOC value of high concentration antibiotic actual waste water gradually decreases, and COD removal rate reaches after illumination 14h
33.24%, TOC removal rate reach 27.65% (raw water COD=206400mg/L, TOC=63750mg/L).It illustrates prepared
Catalyst for practical high concentration antibiotic waste water have good photocatalytic degradation effect.
Fig. 9 is that 1 gained photochemical catalyst of embodiment Pyrogentisinic Acid and sulfanilamide (SN) under the 300W xenon lamp for installing AM1.5 optical filter additional are phonetic
The cyclical stability figure of pyridine photocatalytic degradation.It can be seen from the figure that by five circulation experiments, catalyst Pyrogentisinic Acid and sulfanilamide (SN)
The photocatalytic degradation effect of pyrimidine is not substantially reduced, and illustrates that catalyst is with good stability, reusable.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it would be recognized that above-mentioned
Description be not considered as limitation of the present invention.
Claims (9)
1. a kind of prepare the quantum-dot modified hierarchical porous structure TiO of carbonitride2-SiO2The method of photonic crystal photochemical catalyst, feature
It is, the carbonitride of the catalyst is quantum dot-doped in the skeleton of multistage pore titanium oxide oxidation silicon photonic crystal, specific real
Test that steps are as follows：
1), using urea and sodium citrate as presoma, using low-temperature solid hydro-thermal method, water phase is prepared after dialysis treatment
Carbonitride quantum dot solution；
2), pore creating material is dissolved in organic solution, is stirred, tetrabutyl silicate, inorganic acid, titanium source hydrolysis inhibition are sequentially added
Agent, isopropyl titanate and carbonitride quantum dot solution, obtain mixed solution, and stirring is fed into polystyrene moulding, one
Determine to hydrolyze dry certain time under temperature and humidity, then removes removing template in certain temperature calcining certain time in air, obtain
To the quantum-dot modified hierarchical porous structure TiO of the carbonitride2-SiO2Photonic crystal photochemical catalyst.
2. preparation method according to claim 2, it is characterised in that：The inorganic acid is hydrochloric acid；The concentration of the hydrochloric acid
For 2mol/L-6mol/L, titanium source hydrolysis inhibitor is acetylacetone,2,4-pentanedione.
3. preparation method according to claim 1 to 2, it is characterised in that：The pore creating material is selected from F127, P123.
4. the preparation method as described in claim 1-3, the time of the stirring is 0.5-2h.
5. the preparation method as described in claim 1-4, the temperature of the hydrolysis is 30-60 DEG C, humidity 40-60%.
6. preparation method as claimed in claims 1-5, the temperature of the calcining is 400-600 DEG C；The time of the calcining is
2-6h。
7. the preparation method as described in claim 1-6, which is characterized in that the step 1 is to grind sodium citrate and urea
It is transferred in ptfe autoclave liner, is kept for certain time at 160-200 DEG C after mixing, it is cooling, it separates
The brown solid arrived, then with after dehydrated alcohol supersound washing three times, be fitted into bag filter, dialyses one in deionized water at room temperature
It fixes time, obtains yellowish nitridation carbon quantum dot aqueous solution.
8. the preparation method as described in claim 1-7, which is characterized in that after is EtOH is added in a reservoir in the step 2, then
P123 is added, tetrabutyl silicate (TEOS), HCl, acetyl is added to being completely dissolved to obtain clear solution in stirring in clear solution
Acetone, isopropyl titanate (TTIP) and nitridation carbon quantum dot aqueous solution, stir at room temperature, precursor solution are filled into 300-
In the PS template of 400nm, after hydrolyzing the predetermined time with scheduled temperature and humidity, it is transferred to oven drying, in horse under air atmosphere
It is not calcined in furnace, so that titanium oxide and nitridation carbon quantum dot are compound to get the multistage quantum-dot modified to carbonitride in skeleton
Pore titanium oxide silica photochemical catalyst.
9. a kind of quantum-dot modified hierarchical porous structure TiO of carbonitride2-SiO2Photonic crystal photochemical catalyst, which is characterized in that described
The carbonitride of catalyst is quantum dot-doped in the skeleton of multistage pore titanium oxide oxidation silicon photonic crystal, and the catalyst is by right
It is required that the described in any item preparation methods of 1-8 are prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
| CN105964286A (en) * | 2016-05-18 | 2016-09-28 | 江苏理工学院 | Nitrogen-doped graphene quantum dot and graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
| CN106000440A (en) * | 2016-06-07 | 2016-10-12 | 南昌航空大学 | Preparation method of g-C3N4 quantum dot-loaded titanium dioxide nanoparticles |
| CN106111176A (en) * | 2016-06-21 | 2016-11-16 | 南昌航空大学 | A kind of preparation method of g CNQDs/GO composite photocatalyst material |
| CN106475127A (en) * | 2016-08-30 | 2017-03-08 | 武汉理工大学 | A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof |
-
2018
- 2018-08-02 CN CN201810871692.5A patent/CN108889329B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
| CN105964286A (en) * | 2016-05-18 | 2016-09-28 | 江苏理工学院 | Nitrogen-doped graphene quantum dot and graphite-phase carbon nitride composite photocatalyst and preparation method thereof |
| CN106000440A (en) * | 2016-06-07 | 2016-10-12 | 南昌航空大学 | Preparation method of g-C3N4 quantum dot-loaded titanium dioxide nanoparticles |
| CN106111176A (en) * | 2016-06-21 | 2016-11-16 | 南昌航空大学 | A kind of preparation method of g CNQDs/GO composite photocatalyst material |
| CN106475127A (en) * | 2016-08-30 | 2017-03-08 | 武汉理工大学 | A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| JINGYANG SU ET AL.: ""Self-assembly graphitic carbon nitride quantum dots anchored on TiO2 nanotube arrays: An efficient heterojunction for pollutants degradation under solar light"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| LINLIN ZHANG ET AL.: ""High thermostable ordered mesoporous SiO2–TiO2 coated circulating-bed biofilm reactor for unpredictable photocatalytic and biocatalytic performance"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| MENGQIAO HU ET AL.: ""Ti3+ self-doped mesoporous black TiO2/SiO2/g-C3N4 sheets heterojunctions as remarkable visible-lightdriven photocatalysts"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 杨小龙等: ""TiO2-SiO2二维大孔薄膜的制备及其光催化活性研究"", 《影像科学与光化学》 * |
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