CN101791565B - A TiO2@Graphite Phase Carbon Nitride Heterojunction Composite Photocatalyst and Its Preparation Method - Google Patents
A TiO2@Graphite Phase Carbon Nitride Heterojunction Composite Photocatalyst and Its Preparation Method Download PDFInfo
- Publication number
- CN101791565B CN101791565B CN2010101354293A CN201010135429A CN101791565B CN 101791565 B CN101791565 B CN 101791565B CN 2010101354293 A CN2010101354293 A CN 2010101354293A CN 201010135429 A CN201010135429 A CN 201010135429A CN 101791565 B CN101791565 B CN 101791565B
- Authority
- CN
- China
- Prior art keywords
- tio
- carbon nitride
- graphite phase
- phase carbon
- composite photocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 51
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001912 cyanamides Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 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
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 241001125671 Eretmochelys imbricata Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydroxyl free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920005588 metal-containing polymer Polymers 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005303 weighing 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
Images
Landscapes
- Catalysts (AREA)
Abstract
本发明公开了一种TiO2石墨相氮化碳异质结复合光催化剂及其制备方法，该催化剂结构为：核为TiO2纳米粒子，壳为石墨相氮化碳层。制备方法包括以下步骤：a)通过水热反应制备表面密勒胺包覆的TiO2纳米粒子；b)水洗、分离、干燥后，经煅烧即得TiO2石墨相氮化碳异质结复合光催化剂。该发明具有以下优点：方法简单，成本低，适合大规模工业化生产；该复合光催化具有良好的可见光响应活性及稳定性，可广泛应用于光催化、光电转换等领域。
The invention discloses a TiO2 graphite phase carbon nitride heterojunction composite photocatalyst and a preparation method thereof. The structure of the catalyst is: the core is TiO2 nano particles, and the shell is a graphite phase carbon nitride layer. The preparation method comprises the following steps: a) preparing TiO2 nanoparticles coated with melamine on the surface by hydrothermal reaction; b) washing with water, separating and drying, and then calcining to obtain the TiO2 graphite phase carbon nitride heterojunction composite light catalyst. The invention has the following advantages: the method is simple, the cost is low, and it is suitable for large-scale industrial production; the composite photocatalysis has good visible light response activity and stability, and can be widely used in the fields of photocatalysis, photoelectric conversion and the like.
Description
Technical field
The present invention relates to a kind of TiO
2Graphite phase carbon nitride heterojunction composite photocatalyst and preparation method thereof belongs to photocatalysis field.
Background technology
Along with the continuous development of global process of industrialization, environmental pollution and energy shortage problem are serious day by day, have become the whole world severe challenge to facing altogether.The solar radiation energy is big, and cleanliness without any pollution is inexhaustible, and what use is not the desirable alternative energy source that international community generally acknowledges.Find monocrystalline TiO from Fujishima in 1972 and Honda
2Electrode photodissociation water and Carey etc. are successfully with TiO
2Be used for since the photocatalytic degradation water organic pollution, the conductor photocatalysis technology receives various countries researcher's common concern rapidly owing to can pure utilization pollution-free and inexhaustible solar energy be combined with environmental protection.In in the past 40 years, the oxide of the metal that photocatalysis technology adopts usually or sulfide are as photochemical catalyst, like TiO
2, ZnO
2Deng, it is bigger usually that it prohibits bandwidth, only can utilize the ultraviolet part of sunlight irradiation, and quantum yield is lower, has hindered the practical application of photocatalysis technology.Recently, Wong and Domen etc. have reported a kind of novel no metal-containing polymer semiconductor light-catalyst-graphite phase carbon nitride (g-C
3N
4) under the visible light effect photodissociation water generate hydrogen and oxygen (Wong Xinchen, Nature Mater., 2009,8:76-80) since; The graphite phase carbon nitride has high visible light response activity owing to prohibit bandwidth less (2.7eV), and oxidisability is stronger; Preparation technology is simple, and is cheap, becomes the new direction (Lyth of photochemical catalyst research rapidly; J.Phys.Chem.C, 2009,113:20148-20151; Li, Langmuir, 2009,25:10397-10401; Li, Langmuir, 2010,26:3894-3901).Yet, Domen and Wong etc. further further investigation graphite phase carbon nitride when visible photodissociation water generates oxygen (Domen, J.Phys.Chem.C, 2009,113:4940-4947), find this catalyst under the effect of photohole, self partly decompose and generate N
2Thereby, cause light-catalyzed reaction unstable.Therefore, improving chemical stability, avoid oxidation Decomposition, is that polymer photochemical catalyst-graphite phase carbon nitride moves towards one of key of practical application.
Summary of the invention
The objective of the invention is deficiency, provide a kind of chemical stability good, novel graphite phase carbon nitride composite photo-catalyst of visible light catalytic function admirable and preparation method thereof to above-mentioned graphite phase carbon nitride existence.
The objective of the invention is to realize: a kind of TiO through following mode
2Graphite phase carbon nitride heterojunction composite photocatalyst, the structure of this composite photo-catalyst is: examine and be TiO
2Nano particle, shell are the graphite phase carbon nitride.
TiO
2The crystal formation of nano particle is anatase or rutile or both mixtures.
A kind of TiO
2The preparation method of graphite phase carbon nitride heterojunction composite photocatalyst, preparation process is following:
A) with TiO
2The hydrosol and cyanamide compounds prepare the TiO that surperficial Miller amine coats through hydro-thermal reaction
2Nano particle;
B) to TiO
2After nano particle washing, separation, the drying, promptly get TiO through calcining
2Graphite phase carbon nitride heterojunction composite photocatalyst.
Said cyanamide compounds is meant the mixture of a kind of of cyanamide, double focusing cyanamide or melamine or several kinds.
Hydrothermal reaction condition is: 100 ℃～400 ℃ of reaction temperatures, reaction time 0.5h～50h.
Calcining heat is 300 ℃～1000 ℃, and calcination time is 0.5～10 hour; Be preferably: 400 ℃～800 ℃, calcination time is 1～5 hour.
Calcination atmosphere can be any of air, nitrogen or argon gas.
The present invention has following beneficial effect, and method of the present invention is adopted in (1), can effectively avoid graphite phase carbon nitride self to decompose, and improves chemical stability; (2) through being that the contrast photocatalysis experiment of analogies shows with the parachlorophenol; The graphite phase carbon nitride that composite photo-catalyst of the present invention is purer has higher visible light catalysis activity; Explain that composite photo-catalyst helps the separation of charge of photo-generated carrier, improve quantum yield; (3) preparation technology of the present invention is simple, and the raw material that is adopted is the industrial chemicals of industrial-scale production and cheap, and the composite photo-catalyst cost that therefore adopts method of the present invention to be prepared from is low, and suitable large-scale industrial production.
Fig. 1 is TiO of the present invention
2Graphite phase carbon nitride heterojunction composite photocatalyst structural representation;
Fig. 2 is TiO of the present invention
2The catalytic mechanism sketch map of graphite phase carbon nitride heterojunction composite photocatalyst;
Fig. 3 is TiO of the present invention
2Graphite phase carbon nitride heterojunction composite photocatalyst prepares the process sketch map;
Fig. 4 is the X-ray diffractogram of the embodiment of the invention 1
Fig. 5 is the transmission electron microscope picture of the embodiment of the invention 1;
Fig. 6 is the high-resolution-ration transmission electric-lens figure of the embodiment of the invention 1;
Fig. 7 is the X-ray diffractogram of the embodiment of the invention 2;
Fig. 8 is the high-resolution-ration transmission electric-lens figure of the embodiment of the invention 2
Fig. 9 is the ultraviolet-visible of the embodiment of the invention 2 spectrogram that diffuses;
Figure 10 is the visible light photocatalytic degradation 4-chlorophenol experiment of the embodiment of the invention 2;
The photocatalytic activity stability experiment of Figure 11 embodiment of the invention.
The photocatalytic activity stability experiment of Figure 12 graphite phase carbon nitride.
The specific embodiment
As shown in Figure 1, a kind of TiO
2Graphite phase carbon nitride heterojunction composite photocatalyst, the structure of this composite photo-catalyst is: examine and be TiO
2Nano particle, shell are the graphite phase carbon nitride.
As shown in Figure 2, mechanism of the present invention is following: under light irradiation, and (the g-C of shell graphite phase carbon nitride
3N
4) produce light induced electron, and be injected into TiO
2Conduction band, and and TiO
2The oxygen reaction of surface adsorption generates the superoxide radical spike.Subsequently, from TiO
2Electronics of valence band migration to graphite phase carbon nitride, and at TiO with positive lotus
2Valence band produce the hole, the hole again with the water molecule reaction of absorption, produce the hydroxyl free radical spike.Be of the effect of graphite phase carbon nitride, thereby avoid it, reach the object of the invention by the photohole oxidation to photosensitizer.
As shown in Figure 3, a kind of TiO
2Graphite phase carbon nitride heterojunction composite photocatalyst preparation principle:
Because the nitrogen-atoms band lone electron pair of melamine is with positively charged TiO
2There is electrostatic force in nano particle, is adsorbed to TiO
2The surface of nano particle, under high-temperature and high-pressure conditions, the polycondensation of melamine generation deamination generates Miller amine then, thereby at TiO
2The surface of nano particle forms Miller amine clad.After washing, separation, drying, TiO
2The deamination polycondensation at high temperature further takes place in the Miller amine clad on the surface of nano particle, forms the black phase carbon nitride (g-C of stone
3N
4) layer, promptly get TiO according to the invention
2Graphite phase carbon nitride heterojunction composite photocatalyst.
Following embodiment further specifies of the present invention.
TiO
2The hydrosol can with reference to but and nonessential by the preparation of following method:
Under the vigorous stirring, 10mlTiCl4 is added in the 200ml frozen water, behind about 30Min, rise to room temperature, continue to stir 2h, dialysing to pH value through dialysis membrane then is about 5, can make TiO
2The hydrosol.
Embodiment 1:
The 0.56g melamine is joined 70mlTiO
2Colloidal sol, after stirring and dissolving, ultrasonic 10Min, 100 hydrothermal reaction kettles of packing into then, 180 ℃ of insulation 6h, naturally cool to room temperature then after, centrifugation and with distilled water washing 5 times, 80 ℃ of vacuum drying 12h at 550 ℃ of heat treatment 4h, promptly make TiO then
2Graphite phase carbon nitride heterojunction composite photocatalyst.The X-ray diffraction test shows, as shown in Figure 4: TiO
2Crystalline form is an anatase, calculates according to the Xie Leshi formula, and the about 5nm of its crystal grain, carbonitride are the graphite phase.The high resolution transmission electron microscopy result shows that as shown in Figure 6: catalyst is a nucleocapsid structure, examines to be TiO
2Nano particle, the about 5nm of particle diameter, shell are carbonitride, thick about 2nm.
Embodiment 2:
The 0.56g melamine is joined 70mlTiO
2Colloidal sol, after stirring and dissolving, ultrasonic 10Min, 100 hydrothermal reaction kettles of packing into then, 200 ℃ of insulation 6h, naturally cool to room temperature then after, centrifugation and with distilled water washing 5 times, 80 ℃ of vacuum drying 12h at 550 ℃ of heat treatment 4h, promptly make TiO then
2Graphite phase carbon nitride heterojunction composite photocatalyst.The X-ray diffraction test shows, as shown in Figure 7: TiO
2Crystalline form is an anatase, calculates according to the Xie Leshi formula, and the about 6.2nm of its crystal grain, carbonitride are the graphite phase.The high resolution transmission electron microscopy result shows that as shown in Figure 8: catalyst is a nucleocapsid structure, examines to be TiO
2Nano particle, the about 6nm of particle diameter, shell are carbonitride, thick about 2nm.Ultraviolet-visible diffuse reflection spectrum (Fig. 9) shows that composite photo-catalyst has good absorbent properties to visible light, absorbs sideband and is about 485nm; With the 4-chlorophenol is that the catalytic degradation experiment of simulating pollution thing shows (Figure 10), and this composite photo-catalyst has good visible light catalysis activity, and illumination 60Min can be with 4-chlorophenol degraded 80%.
Embodiment 3:
The 0.84g melamine is joined 70mlTiO
2Colloidal sol, after stirring and dissolving, ultrasonic 10Min, 100 hydrothermal reaction kettles of packing into then, 200 ℃ of insulation 6h, naturally cool to room temperature then after, centrifugation and with distilled water washing 5 times, 80 ℃ of vacuum drying 12h at 550 ℃ of heat treatment 4h, promptly make TiO then
2Graphite phase carbon nitride heterojunction composite photocatalyst.X-ray diffraction test shows: TiO
2Crystalline form is an anatase, calculates according to the Xie Leshi formula, and the about 5.2nm of its crystal grain, carbonitride are the graphite phase.The high resolution transmission electron microscopy result shows: catalyst is a nucleocapsid structure, examines to be TiO
2Nano particle, the about 5nm of particle diameter, shell are carbonitride, thick about 2nm.
Embodiment 4:
The 1.4g melamine is joined 70mlTiO
2Colloidal sol, after stirring and dissolving, ultrasonic 10Min, 100 hydrothermal reaction kettles of packing into then, 200 ℃ of insulation 6h, naturally cool to room temperature then after, centrifugation and with distilled water washing 5 times, 80 ℃ of vacuum drying 12h at 520 ℃ of heat treatment 4h, promptly make TiO then
2Graphite phase carbon nitride heterojunction composite photocatalyst.X-ray diffraction test shows: TiO
2Crystalline form is an anatase, calculates according to the Xie Leshi formula, and the about 5nm of its crystal grain, carbonitride are the graphite phase.The high resolution transmission electron microscopy result shows: catalyst is a nucleocapsid structure, examines to be TiO
2Nano particle, the about 5nm of particle diameter, shell are carbonitride, thick about 2nm.
Embodiment 5:
The 2.8g melamine is joined 70mlTiO
2Colloidal sol, after stirring and dissolving, ultrasonic 10Min, 100 hydrothermal reaction kettles of packing into then, 220 ℃ of insulation 6h, naturally cool to room temperature then after, centrifugation and with distilled water washing 5 times, 80 ℃ of vacuum drying 12h at 530 ℃ of heat treatment 4h, promptly make TiO then
2Graphite phase carbon nitride heterojunction composite photocatalyst.X-ray diffraction test shows: TiO
2Crystalline form is an anatase, calculates according to the Xie Leshi formula, and the about 4.8nm of its crystal grain, carbonitride are the graphite phase.The high resolution transmission electron microscopy result shows: catalyst is a nucleocapsid structure, examines to be TiO
2Nano particle, the about 5nm of particle diameter, shell are carbonitride, thick about 3nm.
The catalyst activity stability experiment:
Reference literature (Li, Langmuir, 2009,25:10397-10401), the 5g melamine at 550 ℃ of heat treatment 4h, is prepared pure graphite phase carbon nitride photochemical catalyst.
Accurately take by weighing pure graphite phase carbon nitride of 100mg and embodiment 2 prepared composite catalyst respectively, be added to 200ml 0.3 * 10
-4In the 4-chlorophenol aqueous solution of M, ultrasonic 5Min is after lucifuge stirs 1h; Adopting the 300W xenon lamp is analog light source; The following light of filtering 420nm wavelength is taken a sample behind the certain hour at interval, is flowing phase with methyl alcohol/deionized water (40: 60); Flow velocity 1ml/Min adopts residual 4-chlorophenol concentration in the high-performance liquid chromatogram determination solution.
Then with the centrifugal recovery of photochemical catalyst, 80 ℃ of dryings 6 hours.By above operation, reuse 4 times, carry out the catalyst activity stability experiment, like Figure 11, shown in 12.Visible from scheming: prepared composite photochemical catalyst of the present invention is under visible light irradiation, and 60Min is the 4-chlorophenol of degradable about 80%, and under the same terms, pure graphite phase carbon nitride can only degrade about 35%.In addition, with the increase of photochemical catalyst access times, pure graphite phase carbon nitride catalytic activity descends gradually; After reusing 4 times; At only can degrade about 25% 4-chlorophenol of visible light irradiation 60Min, and under the same terms, composite photo-catalyst still can keep about 80% degradation rate.The result shows that prepared composite photochemical catalyst of the present invention not only has good visible light catalysis activity, also has good stable property simultaneously.
Claims (7)
1. TiO
2Graphite phase carbon nitride heterojunction composite photocatalyst is characterized in that: the structure of this composite photo-catalyst is: examine and be TiO
2Nano particle, shell are the graphite phase carbon nitride.
2. according to the said a kind of TiO of claim 1
2Graphite phase carbon nitride heterojunction composite photocatalyst is characterized in that: TiO
2The crystal formation of nano particle is anatase or rutile or both mixtures.
3. a kind of TiO according to claim 1
2The preparation method of graphite phase carbon nitride heterojunction composite photocatalyst, it is characterized in that: preparation process is following:
A) with TiO
2The hydrosol and cyanamide compounds prepare the TiO that surperficial Miller amine coats through hydro-thermal reaction
2Nano particle;
B) to TiO
2After nano particle washing, separation, the drying, promptly get TiO through calcining
2Graphite phase carbon nitride heterojunction composite photocatalyst.
4. according to the said a kind of TiO of claim 3
2The preparation method of graphite phase carbon nitride heterojunction composite photocatalyst is characterized in that: said cyanamide compounds is meant the mixture of a kind of of cyanamide, double focusing cyanamide or melamine or several kinds.
5. according to the said a kind of TiO of claim 3
2The preparation method of graphite phase carbon nitride heterojunction composite photocatalyst is characterized in that: hydrothermal reaction condition is: 100 ℃～400 ℃ of reaction temperatures, reaction time 0.5h～50h.
6. according to the said a kind of TiO of claim 3
2The preparation method of graphite phase carbon nitride heterojunction composite photocatalyst is characterized in that: calcining heat is 300 ℃～1000 ℃, and calcination time is 0.5～10 hour.
7. according to the said a kind of TiO of claim 3
2The preparation method of graphite phase carbon nitride heterojunction composite photocatalyst is characterized in that: calcination atmosphere can be any of air, nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101354293A CN101791565B (en) | 2010-03-30 | 2010-03-30 | A TiO2@Graphite Phase Carbon Nitride Heterojunction Composite Photocatalyst and Its Preparation Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101354293A CN101791565B (en) | 2010-03-30 | 2010-03-30 | A TiO2@Graphite Phase Carbon Nitride Heterojunction Composite Photocatalyst and Its Preparation Method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101791565A CN101791565A (en) | 2010-08-04 |
| CN101791565B true CN101791565B (en) | 2012-04-25 |
Family
ID=42584610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101354293A Expired - Fee Related CN101791565B (en) | 2010-03-30 | 2010-03-30 | A TiO2@Graphite Phase Carbon Nitride Heterojunction Composite Photocatalyst and Its Preparation Method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101791565B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125863A (en) * | 2011-01-27 | 2011-07-20 | 湘潭大学 | Preparation method of graphite phase carbon nitride/rutile monocrystal titanium dioxide (TiO2) nanowire array |
| CN102698784B (en) * | 2012-06-13 | 2014-07-23 | 浙江师范大学 | Visible light response catalyst and preparation method thereof |
| CN102974377B (en) * | 2012-09-27 | 2014-11-26 | 清华大学 | Carbon-nitrogen alkene photocatalyst and preparation method thereof |
| CN102950016B (en) * | 2012-10-29 | 2014-04-09 | 华东理工大学 | A kind of preparation method of ZnO/g-C3N4 composite photocatalyst |
| CN102962088A (en) * | 2012-11-06 | 2013-03-13 | 中国科学院广州地球化学研究所 | Composite visible light catalyst of TiO2 microspheres and g-C3N4 and its preparation method and application |
| CN103041772A (en) * | 2012-11-22 | 2013-04-17 | 湘潭大学 | One-dimensional zinc oxide/graphitized carbon core-shell structure hetero-junction and preparation method thereof |
| CN103143380B (en) * | 2013-03-21 | 2015-01-07 | 哈尔滨工业大学 | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material |
| CN104043471A (en) * | 2014-07-02 | 2014-09-17 | 东华大学 | A kind of preparation method of graphene/Ta3N5 composite photocatalyst |
| CN106824246B (en) * | 2014-11-06 | 2019-08-27 | 江苏理工学院 | TiO 22/g-C3N4Preparation method of composite visible light catalyst |
| CN104549403A (en) * | 2014-11-28 | 2015-04-29 | 阜阳师范学院 | A kind of composite photocatalyst DyVO4/g-C3N4 and its preparation method |
| CN104646046B (en) * | 2015-03-11 | 2017-08-01 | 湖南大学 | A kind of method of selective oxidation cyclohexane |
| CN104722324A (en) * | 2015-04-02 | 2015-06-24 | 南昌航空大学 | Three-step method for preparing Ag-g-C3N4/TiO2 ternary compound |
| CN104801328B (en) * | 2015-04-21 | 2017-05-17 | 河北科技大学 | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature |
| CN105056981B (en) * | 2015-07-16 | 2017-05-17 | 南昌航空大学 | Preparation and application of composite photocatalyst g-C3N4-BiFeO3 for efficiently removing persistent organic pollutants |
| CN106732712A (en) * | 2016-11-11 | 2017-05-31 | 天津大学 | The synthetic method of the graphite phase carbon nitride homotype heterojunction photocatalysis material with multi-level structure and application |
| CN107413364B (en) * | 2017-05-03 | 2021-02-12 | 中国科学院东北地理与农业生态研究所 | Preparation method and application of titanium dioxide-coated graphite-phase carbon nitride composite photocatalyst with hollow mesoporous core-shell structure |
| CN107326394B (en) * | 2017-06-09 | 2019-10-11 | 常州大学 | A method for preparing carbon nitride modified titanium dioxide photoanode with core-shell structure |
| CN107213912B (en) * | 2017-06-16 | 2020-05-19 | 益阳医学高等专科学校 | Composite nano material and preparation method and application thereof |
| CN107456987B (en) * | 2017-08-06 | 2020-01-10 | 武汉轻工大学 | Method for preparing carbon nitride/titanium dioxide heterojunction photocatalyst by electrostatic spinning one-step method |
| CN108380234A (en) * | 2018-03-07 | 2018-08-10 | 苏州宝澜环保科技有限公司 | A kind of carbon-based semiconductors composite material and preparation method |
| CN109713153B (en) * | 2018-11-21 | 2020-07-24 | 云谷（固安）科技有限公司 | Organic light emitting diode unit, display panel and method of making the same |
| CN109626422A (en) * | 2018-12-11 | 2019-04-16 | 辽宁大学 | A kind of TiO2/g-C3N4The preparation method and applications of light anode nanocomposite |
| CN110368893B (en) * | 2019-08-22 | 2022-11-08 | 扬州大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
| CN110639583A (en) * | 2019-09-05 | 2020-01-03 | 中南民族大学 | Preparation method of high-activity and high-stability catalyst for Fischer-Tropsch synthesis reaction |
| CN112993231A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Carbon-sulfur composite electrode and preparation and application thereof |
| CN111994992A (en) * | 2020-07-16 | 2020-11-27 | 广东工业大学 | Method for killing red tide algae by using supported composite photocatalyst |
| CN112264075B (en) * | 2020-11-09 | 2022-08-26 | 华侨大学 | High-efficiency demercuration photocatalyst suitable for medium-low temperature condition and preparation method thereof |
| CN113582324A (en) * | 2021-08-11 | 2021-11-02 | 哈尔滨工业大学 | Method for removing organic pollutants in water by using sunlight |
| CN115260682B (en) * | 2022-07-25 | 2024-02-06 | 山东农业大学 | Preparation method of recyclable and renewable photocatalytic preservative film |
| CN116920912A (en) * | 2023-07-27 | 2023-10-24 | 华北科技学院(中国煤矿安全技术培训中心) | Preparation method of graphite phase carbon nitride/titanium dioxide composite photocatalyst |
| CN118002173A (en) * | 2024-01-30 | 2024-05-10 | 天津市职业大学 | A carbon nitride-titanium dioxide composite photocatalyst and preparation method thereof |
-
2010
- 2010-03-30 CN CN2010101354293A patent/CN101791565B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101791565A (en) | 2010-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101791565B (en) | A TiO2@Graphite Phase Carbon Nitride Heterojunction Composite Photocatalyst and Its Preparation Method | |
| Zhang et al. | Hierarchical Z-scheme gC 3 N 4/Au/ZnIn 2 S 4 photocatalyst for highly enhanced visible-light photocatalytic nitric oxide removal and carbon dioxide conversion | |
| Liu et al. | Easily and synchronously ameliorating charge separation and band energy level in porous g-C3N4 for boosting photooxidation and photoreduction ability | |
| Xu et al. | Size-dependent Mie’s scattering effect on TiO2 spheres for the superior photoactivity of H2 evolution | |
| Qi et al. | Constructing CeO 2/nitrogen-doped carbon quantum dot/gC 3 N 4 heterojunction photocatalysts for highly efficient visible light photocatalysis | |
| CN107159313B (en) | Preparation method of a core-shell structured TiO2 nanotube @Ti-MOF catalyst | |
| Zhu et al. | Carbon nitride-modified defective TiO2–x@ Carbon spheres for photocatalytic H2 evolution and pollutants removal: synergistic effect and mechanism insight | |
| CN102500388B (en) | Copper and bismuth co-doped nano titanium dioxide photocatalyst and preparation and application thereof | |
| CN101792117B (en) | Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder | |
| CN106492854B (en) | There is the composite nano Ag of photocatalysis performance using two-step method preparation3PO4/TiO2Material and methods and applications | |
| CN102107138B (en) | Photocatalyst, preparation method and application thereof | |
| CN101347724B (en) | A kind of carbon 60/titanium dioxide nanocomposite photocatalyst and its preparation method and application | |
| Wang et al. | When MoS 2 meets TiO 2: facile synthesis strategies, hybrid nanostructures, synergistic properties, and photocatalytic applications | |
| CN103285861B (en) | An Ag3VO4/TiO2 compound nano-wire having visible light activity, a preparation method and applications thereof | |
| Zhao et al. | Mesoporous Cu–Cu 2 O@ TiO 2 heterojunction photocatalysts derived from metal–organic frameworks | |
| CN105214656A (en) | Gold nano cluster-golden nanometer particle-titanium dioxide composite photocatalyst and application | |
| CN102963934A (en) | Preparation method of bismuth tungstate quantum dot and preparation method of bismuth tungstate quantum dot-graphene composite material | |
| CN101966452B (en) | A Preparation Method of LaVO4 and TiO2 Composite Nanotubes Responsive to Visible Light | |
| CN101786005A (en) | Method for preparing cadmium sulfide-titanium dioxide nano-tube composite catalyst | |
| CN105771948A (en) | Double-shell titanium dioxide catalyst with high photocatalytic hydrogen generation performance and preparation method thereof | |
| CN106268902B (en) | A kind of preparation method of g-C3N4 quantum dot, Ag quantum dot sensitized BiVO4 photocatalyst | |
| CN106944074A (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| Rabin et al. | A procession on photocatalyst for solar fuel production and waste treatment | |
| CN101602008B (en) | Nano-material composite visible light catalyst and preparation method thereof | |
| Yue et al. | A facile synthesis method of TiO2@ SiO2 porous core shell structure for photocatalytic hydrogen evolution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120425 Termination date: 20180330 |