CN108355693A - High Efficiency Superfine TiO2The preparation of nano particle/graphite phase carbon nitride nanometer sheet composite photo-catalyst - Google Patents
High Efficiency Superfine TiO2The preparation of nano particle/graphite phase carbon nitride nanometer sheet composite photo-catalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 title abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910010062 TiCl3 Inorganic materials 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000004887 air purification Methods 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 241001074085 Scophthalmus aquosus Species 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 phenyl compound Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
High Efficiency Superfine TiO2The preparation of nano particle/graphite phase carbon nitride nanometer sheet composite photo-catalyst, belongs to catalysis material technical field.With TiCl3For titanium source, using graphite phase carbon nitride nanometer sheet as carrier, alcohol is solvent, and hydro-thermal 1 12 hours, the superfine Ti O of acquisition are carried out in 70 180 DEG C of water heating kettle2Nano particle is equably supported on graphite phase carbon nitride nanometer sheet surface, forms composite photo-catalyst.The composite photo-catalyst has higher specific surface area and higher photocatalytic activity.The catalyst is dispersed in sewage, or coated in substrate, the pollutant in water removal and in air is effectively removed under sunlight.Therefore it can be used for building, indoor wall, surface of vehicle, the carrier surfaces such as windowpane are as automatic cleaning coating and pollutant elimination, and indoor air purification, open-air purification all has preferable effect, while also having the function of preferable antibiotic and sterilizing.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of superfine titanic oxide nano particle/graphite-phase
The preparation method of the composite photo-catalyst of azotized carbon nano piece.
Background technology
Photochemical catalyst can absorb sunlight as a kind of semi-conducting material, generate the electrons and holes of photoproduction, photoproduction electricity
It is sub that there is reduction characteristic, it is reacted with oxygen molecule and generates superoxide radical, photohole produces hydroxyl certainly with water molecule reaction
All there is very strong oxidability by base and photohole, be referred to as active oxygen radical.These free radicals have very
Strong oxidability, can be with the oxysulfide (SOx) in oxidation air, nitrogen oxides (NOx), volatile organic compound
(VOC), so that these pollutants is further oxided and achieve the purpose that air purification.In addition, this photochemical catalyst in water can be with
Oxidative degradation removes the Trace Organic Compounds dissolved in water, such as phenyl compound, and halogen-containing compound can also utilize light
Heavy metal in raw electron reduction aqueous solution and generated living radical, kill the microorganism and bacterium in water, to
Achieve the purpose that purification of water quality.When TiO2Photocatalyst coating is when in substrate, TiO under light illumination2Surface becomes super hydrophilic
Surface, therefore when drop in TiO2Surface can form water membrane, rather than independent drop can in conjunction with strong oxidation performance
It is self-cleaning to play the role of as self-cleaning coating applied to the outer surface of skyscraper and the surface of windowpane.
However, when using TiO2Must be under ultraviolet light since it is only capable of absorbing ultraviolet light as photochemical catalyst
Its light-catalysed function of competence exertion, and only containing 5% ultraviolet light in sunlight, 40% visible light and 55% it is infrared
Light.Therefore TiO2Sunlight cannot fully be utilized.Nearest king's heart morning etc. finds that the carbonitride of graphite-phase is a kind of no metal light
Catalyst, which not only has the photocatalysis performance of efficient stable, but also also has light-catalysed performance in visible region
(Nat.Mater.2009,).It, can be with due to the difference of the two energy level when two kinds of semiconductors couplings form heterojunction structure together
Promote photogenerated charge to shift, so as to cause being spatially separating for electrons and holes, avoids the again compound of electrons and holes, reach
To the purpose for improving photocatalysis performance
Invention content
One of the objects of the present invention is to provide a kind of superfine Ti O2Nano particle/graphite phase carbon nitride composite photocatalyst
Synthetic method, the preparation method is simple and practical, wherein TiO2Particle size is less than 10nm, nano-lamellar structure is presented in carbonitride,
Specific surface area is higher, photocatalysis performance is excellent, can be applied to the processing of waste water and exhaust gas, the purification of room air and antibacterial material
Material.
In order to achieve the above objectives, the present invention uses following technical scheme：
A kind of superfine Ti O2The synthetic method of nano particle/graphite phase carbon nitride, by TiCl3Solution is added in ethyl alcohol, so
A certain amount of carbonitride is added in above-mentioned solution afterwards, dispersion liquid is transferred in hydrothermal reaction kettle by ultrasonic disperse 30 minutes,
It is reacted 1-12 hours at 70-180 DEG C, collects the pale yellow precipitate that reaction generates, then carry out ethyl alcohol washing, drying can obtain
To composite photo-catalyst, it is characterised in that is obtained is less than 10 nanometers of TiO2Nano particle is directly loaded in azotized carbon nano
On piece.And obtained catalyst has higher specific surface area (~241m2/ g) and higher photocatalytic activity.
Wherein TiO2Crystal form can by reaction condition control be anatase phase or rutile phase, by making
Raw material is added or is added without SnCl when standby4The reaction condition control rutile phase or anatase phase of aqueous solution.Further
Preferably Rutile Type TiO2Nanometer rods or Anatase TiO2Nano spherical particle.
Preferably, per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution correspondence, which is added in 60 milliliters of ethyl alcohol, is reacted,
90-150 milligrams of azotized carbon nano piece is added in above-mentioned solution, and ultrasonic disperse 30 minutes is then transferred into hydrothermal reaction kettle
Middle reaction keeps the temperature 1-12 hours at 70-180 DEG C, and faint yellow solid is collected after reaction, and centrifugation, washing, drying obtain TiO2It is spherical
The composite photo-catalyst of nano-particle and graphite phase carbon nitride.
Preferably, per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution corresponds to the SnCl of 1-4 milliliters of 0-1M (preferably 0.5M)4Water
Solution and 60 milliliters of ethyl alcohol, 90-150 milligrams of azotized carbon nano piece are added in above-mentioned solution, ultrasonic disperse 30 minutes, then
It is transferred in hydrothermal reaction kettle and reacts, 1-12 hours are kept the temperature at 70-180 DEG C, faint yellow solid is collected after reaction, centrifuge, wash,
Drying obtains TiO2Nanometer rods/nitridation carbon composite photocatalyst.
The method overcome the expensive disadvantages of metatitanic acid organic ester, and do not need complicated washing step and can be obtained
The solid powder of titanium dioxide superfine nano particle/carbonitride composite catalyst.
With the TiO2Nano particle/graphite phase carbon nitride nanometer sheet composite photo-catalyst, which is main functional component, to be used for
Develop the nano paint with photocatalytic activity.The catalyst is dispersed in sewage, or is coated in substrate, in sunlight
Water removal is effectively gone to neutralize the pollutant in air down.Therefore it can be used for building, indoor wall, surface of vehicle, windowpane etc.
Carrier surface is eliminated as automatic cleaning coating and pollutant, indoor air purification, and open-air purification all has preferable effect
Fruit, while also having the function of preferable antibiotic and sterilizing.
Beneficial effects of the present invention are as follows：
1, the present invention provides a kind of simple, cheap methods to prepare the TiO of anatase2Nano-particle and rutile are brilliant
The TiO of phase2The synthetic method of nanometer rods and nitridation carbon composite photocatalyst.
2, TiO of the invention2Nano particle/graphite phase carbon nitride nanometer sheet can be used for preparing efficiently having photocatalysis
The coating of performance realizes the purification to pollutant and air under sunlight or ultraviolet light.
Description of the drawings
Fig. 1 are the composite catalyst obtained in embodiment 1, pure TiO2The XRD diagram of nanometer rods and pure graphite phase carbon nitride
Case, center line 1 are rutile TiO2Nanometer rods, line 2 are the TiO for the Rutile Type that embodiment 1 obtains2Nanometer rods/graphite-phase nitridation
Carbon nanosheet, line 3 are pure graphite phase carbon nitride.
Fig. 2 is the TiO that embodiment 1 obtains2The transmission electron microscope of nanometer rods/graphite phase carbon nitride nanometer sheet composite catalyst.
Fig. 3 is the composite catalyst obtained in embodiment 2, pure TiO2The XRD diagram of nano particle and pure graphite phase carbon nitride
Case, center line 1 are anatase TiO2Nano particle, line 2 are the TiO for the anatase that embodiment 2 obtains2Nano particle/graphite-phase nitrogen
Change carbon nanosheet, line 3 is pure graphite phase carbon nitride.
Fig. 4 is the TiO that embodiment 2 obtains2The transmission electron microscope of nano-particle and the size distribution plot of nano-particle.
Fig. 5 is TiO2Nanometer rods, the nitrogen adsorption desorption curve in pure graphite phase carbon nitride nanometer sheet and embodiment 3.
Fig. 6 is the TiO that embodiment 1 obtains2The TiO that nano-particle (line 2), embodiment 3 obtain2Nanometer rods (line 3) and quotient
Product P25TiO2The photocatalytic degradation rhodamine B curve under the illumination of full spectrum of nano particle (line 1).A is rhodamine B drop
The change curve of rhodamine B concentration in solution preocess, b are corresponding degradation reaction rate curves.
Fig. 7 contrast samples (P25TiO2, TiO2Composite photo-catalyst exists in nanometer rods, purity nitrogen carbon nanosheet and embodiment 3
The design sketch (a) of rhodamine B degradation and degradation kinetics rate diagram (b) under visible light.
Fig. 8 is comparative catalyst TiO2Nanometer rods, graphite phase carbon nitride nanometer sheet and composite catalyst (embodiment 4) are complete
The design sketch of degradation of phenol under spectrum (a) and visible light (b).Composite catalyst shows higher catalytic activity.(c) Pyrogentisinic Acid
Mineralising result figure, (d) be catalyst stability test.
Specific implementation mode
In order to better illustrate the present invention, with reference to embodiment and attached drawing, the present invention will be further described, but this hair
It is bright to be not limited to following embodiment.It is preferred that 15-20wt%TiCl3Aqueous solution is：TiCl3It is dissolved in the hydrochloric acid solution of 30wt%,
TiCl3A concentration of 15-20wt%.
50 grams of urea, thiocarbamide, dicyandiamide or melamine are placed in crucible, heated in Muffle furnace, with 0.1-10
DEG C/min the rate of heat addition, and kept for 1-5 hours at 500-600 DEG C, the solid powder obtained is graphite phase carbon nitride.
Embodiment 1
TiO2The preparation method of nanometer rods/graphite phase carbon nitride nanometer sheet composite catalyst:
1. by the TiCl of 2 milliliters of 15-20%3The SnCl of aqueous solution and 1 milliliter of 0.5M4Aqueous solution is added to 60 milliliters of second
In alcohol, 90 milligrams of azotized carbon nano piece is added in above-mentioned solution, then above-mentioned solution is transferred to by ultrasonic disperse 30 minutes
In 100 milliliters of hydrothermal reaction kettle, places it in convection oven and be warming up to 100 DEG C and be maintained at 100 DEG C 4 hours, then
Natural cooling.
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant is removed by centrifugation, obtains solid.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed
TiCl3It removes, is then centrifuged for, obtain solid.
It is dried 4. the solid obtained in step 3 is put into 70 DEG C of baking ovens, drying acquisition TiO in case2Nanometer rods/graphite-phase
Azotized carbon nano piece composite catalyst powder about 210mg.
Line 1 in Fig. 1 is to obtain TiO2The pattern of the XRD of nanometer rods, line 3 are the XRD diagram case of pure graphite phase carbon nitride, line
2 be TiO2The XRD diagram case of nanometer rods/graphite phase carbon nitride nanometer sheet composite catalyst, it can be seen that the TiO obtained2Nanometer rods
For rutile phase.Graphite phase carbon nitride is lamellar structure, and composite catalyst has carbonitride and Rutile Type TiO2Typical case
XRD diffraction patterns.Fig. 2 is is obtained TiO2The transmission electron microscope picture of nanometer rods/graphite phase carbon nitride nanometer sheet composite catalyst with
And size distribution plot.It can be seen that obtained TiO from low power transmission electron microscope picture2It is in mainly rodlike.A diameter of 1.5 nanometers, stick
It is about 8 nanometers long.The lattice dimensions that can see in high resolution electron microscopy figure are 0.324 nanometer, this is rutile TiO2
(111) lattice dimensions.This also demonstrates obtained TiO2Nano particle is rutile phase.And carbonitride is nanoscale twins knot
Structure.Simultaneously it can be seen that TiO2Nanometer sheet is uniformly dispersed in azotized carbon nano on piece, does not assemble significantly.
Embodiment 2TiO2The preparation method of nano particle/graphite phase carbon nitride nanometer sheet composite catalyst：
1. by the TiCl of 2 milliliters of 15-20wt%3Aqueous solution is added in 60 milliliters of ethyl alcohol, and is stirred at room temperature 30
Minute.Then above-mentioned solution is transferred in 100 milliliters of hydrothermal reaction kettle, places it in convection oven and is warming up to 100 DEG C
And it is maintained at 100 DEG C 6 hours, natural cooling.
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant is removed by centrifugation, obtains solid.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed
TiCl3It removes, is then centrifuged for, obtain solid.
4. the solid obtained in step 3, which is put into drying in 70 DEG C of baking ovens, obtains TiO2Nano particle/graphite phase carbon nitride
Nanometer sheet composite catalyst powder about 200mg.
Line 1 in Fig. 3 is to obtain TiO2The pattern of the XRD of nano particle, line 3 are the XRD diagram case of pure graphite phase carbon nitride,
Line 2 is TiO2The XRD diagram case of nano particle/graphite phase carbon nitride nanometer sheet composite catalyst, it can be seen that the TiO obtained2It receives
Rice grain is anatase phase.Graphite phase carbon nitride is lamellar structure, and composite catalyst has carbonitride and Anatase TiO2
Typical XRD diffraction patterns.Fig. 4 is is obtained TiO2The transmission electron microscope picture and size distribution plot of nano particle.It can be seen that
The TiO obtained2The size of nano particle is about 2-10 nanometers, and the lattice dimensions that can see in high resolution electron microscopy figure are
0.346 nanometer, this is Detitanium-ore-type TiO2(101) lattice dimensions.This also demonstrates obtained TiO2Nano particle is anatase.
Embodiment 3
TiO2The preparation method of nanometer rods/graphite phase carbon nitride nanometer sheet composite catalyst
1. by the TiCl of 4 milliliters of 15-20%3The SnCl of aqueous solution and 2 milliliters of 0.5M4Aqueous solution is added to 60 milliliters of second
In alcohol, 120 milligrams of azotized carbon nano piece is added in above-mentioned solution, then ultrasonic disperse 30 minutes shifts above-mentioned solution
Into 100 milliliters of hydrothermal reaction kettles, places it in convection oven and be warming up to 100 DEG C and be maintained at 100 DEG C 4 hours, so
Natural cooling afterwards..
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant is removed by centrifugation, obtains solid.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed
TiCl3It removes, is then centrifuged for, obtain solid.
It is dried 4. the solid obtained in step 3 is put into 70 DEG C of baking ovens, drying acquisition TiO in case2Nanometer rods/graphite-phase
Azotized carbon nano piece composite catalyst powder about 300mg.
Fig. 5 is obtained TiO2Nanometer rods, the N of graphite phase carbon nitride nanometer sheet and the two composite catalyst2Adsorption desorption is bent
Line, it can be seen that all adsorption desorption curves are typical typeIV curves, that is to say, that there are mesoporous.It is received in 3-5 in its aperture
Rice range.Its BET specific surface area is respectively 312m2/ g, 110m2/ g and 241m2/ g can be seen that obtained TiO2 nanometer rods/
Graphite phase carbon nitride has higher specific surface area.
Embodiment 4
TiO2The preparation method of nanometer rods/graphite phase carbon nitride nanometer sheet composite catalyst
1. by the TiCl of 4 milliliters of 15-20%3The SnCl of aqueous solution and 2 milliliters of 0.5M4Aqueous solution is added to 60 milliliters of second
In alcohol, 150 milligrams of azotized carbon nano piece is added in above-mentioned solution, then ultrasonic disperse 30 minutes shifts above-mentioned solution
Into 100 milliliters of hydrothermal reaction kettles, places it in convection oven and be warming up to 120 DEG C and be maintained at 120 DEG C 4 hours, so
Natural cooling afterwards.
2. the dispersion liquid obtained in step 1 is put in centrifuge tube, supernatant is removed by centrifugation, obtains solid.
3. 10 milliliters of ethanol solution is added in the solid obtained in step 2, ultrasound, will be unreacted to being completely dispersed
TiCl3It removes, is then centrifuged for, obtain solid.
It is dried 4. the solid obtained in step 3 is put into 70 DEG C of baking ovens, drying acquisition TiO in case2Nanometer rods/graphite-phase
Azotized carbon nano piece composite catalyst powder about 280mg.
Fig. 6 is obtained TiO2The design sketch (a) and drop of the photocatalytic degradation rhodamine B of nanometer rods/graphite phase carbon nitride
Solve kinetic rate (b).The degradation rate of composite photo-catalyst is above simple TiO2With the degradation rate of carbonitride, this says
Bright it can be seen from the figure that, composite photo-catalyst possess better photocatalytic activity.In the TiO of different proportion2It is compound with carbonitride
In catalyst, the sample of embodiment 3 shows optimal catalytic performance.
Fig. 7 contrast samples (P25TiO2, TiO2Composite photo-catalyst exists in nanometer rods, purity nitrogen carbon nanosheet and embodiment 3
The design sketch (a) of rhodamine B degradation and degradation kinetics rate diagram (b) under visible light.It can be seen that compound under visible light urge
Agent still shows higher catalytic activity.
Fig. 8 is comparative catalyst TiO2Nanometer rods, graphite phase carbon nitride nanometer sheet and composite catalyst in full spectrum (a) and
The design sketch of degradation of phenol under visible light (b).Composite catalyst shows higher catalytic activity.(c) the mineralising knot of Pyrogentisinic Acid
Fruit is schemed, it can be seen that composite catalyst can effectively remove the organic matter in water.(d) be catalyst stability test, can
After finding out catalyst cleaning 3 cycles, higher catalytic activity is still kept.
The above embodiment of the present invention only examples made by the present invention to clearly illustrate, are not to embodiment of the present invention
Restriction.The obvious variation amplified out on the basis of the above description is still in protection scope of the present invention.
Claims (5)
1. a kind of superfine Ti O2The synthetic method of nano particle/graphite phase carbon nitride nanometer sheet, which is characterized in that by TiCl3Solution
Hydrochloric acid solution is added in ethyl alcohol, and graphite phase carbon nitride nanometer sheet is then added, and ultrasonic disperse 30 minutes is then anti-by hydro-thermal
Pale yellow precipitate should be obtained, ethyl alcohol washing is then carried out, drying can be obtained ultra-fine nano particle, the TiO obtained2Nanometer
The size of particle is directly loaded less than 10 nanometers in miscellaneous graphite phase carbon nitride nanometer sheet, obtains composite catalyst.
2. a kind of superfine Ti O described in accordance with the claim 12The synthetic method of nano particle/graphite phase carbon nitride nanometer sheet,
It is characterized in that, the synthesis of graphite phase carbon nitride nanometer sheet：By 50 grams of urea, thiocarbamide, dicyandiamide or melamine place crucible
In, it is heated in Muffle furnace, with 0.1-10 DEG C/min of the rate of heat addition, and is kept for 1-5 hours, obtained at 500-600 DEG C
Solid powder is graphite phase carbon nitride.
3. a kind of superfine Ti O described in accordance with the claim 12The synthetic method of nano particle/graphite phase carbon nitride nanometer sheet,
It is characterized in that, crystal form is anatase phase or rutile phase by reaction condition control, is added by raw material in the preparation
Enter or be added without SnCl4The reaction condition control anatase phase or rutile phase of aqueous solution.
4. a kind of superfine Ti O described in accordance with the claim 32The synthetic method of nano particle/graphite phase carbon nitride nanometer sheet,
It is characterized in that, per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution correspondence, which is added in 60 milliliters of ethyl alcohol, is reacted, 90-150 millis
Gram graphite phase carbon nitride be added in above-mentioned solution, ultrasonic disperse 30 minutes, then alcohol thermal response 1- is kept the temperature at 70-180 DEG C
12 hours, centrifugation, washing, drying obtained TiO2The composite catalyst of nano spherical particle and carbonitride；
Or per 1-4 milliliters of 15-20wt%TiCl3Aqueous solution corresponds to the SnCl of 1-4 milliliters of 0-1M (being not 0)4Aqueous solution and 60 milliliters
Ethyl alcohol, is added 90-150 milligrams of carbonitride, ultrasonic disperse 30 minutes, and then it is small to keep the temperature 1-12 at 70-180 DEG C for alcohol thermal response
When, centrifugation, washing, drying obtain TiO2Nanometer rods, gained TiO2Nanometer rods and carbonitride composite catalyst.
5. the superfine Ti O being prepared according to claim 1-4 any one of them methods2Nano particle with carbonitride is compound urges
Agent.
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| CN113244960A (en) * | 2021-05-24 | 2021-08-13 | 南京工业大学 | High-hydrophobicity TiO suitable for low-temperature plasma2@ ZIF-8 catalyst and preparation method and application thereof |
| CN113856757A (en) * | 2021-11-04 | 2021-12-31 | 广东工业大学 | Polydopamine-modified carbon nitride/titanium dioxide-loaded foam nickel composite photocatalyst and preparation method and application thereof |
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| CN114433048A (en) * | 2022-01-20 | 2022-05-06 | 内蒙古农业大学 | In-situ stripping preparation C3N4/TiO2(B) Method and application of micron flower composite catalyst |
| CN115069283A (en) * | 2022-05-20 | 2022-09-20 | 青岛科技大学 | Multi-element doped porous carbon nanosheet composite two-phase TiO 2 Method for preparing hemisphere |
| CN115069283B (en) * | 2022-05-20 | 2023-07-21 | 青岛科技大学 | Multi-element doped porous carbon nano-sheet composite two-phase TiO 2 Method for preparing hemisphere |
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