CN105903486B - A kind of Z-type photochemical catalyst and preparation method thereof - Google Patents
A kind of Z-type photochemical catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000004408 titanium dioxide Substances 0.000 claims description 21
- -1 iron ion Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 230000004044 response Effects 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to photocatalysis technology field, especially a kind of preparation method of photochemical catalyst includes the following steps: titanium precursors, alcoholic solvent, acid and iron ion and g- carbonitride being mixed to form mixture in proportion；The mass ratio of the g- carbonitride and the titanium precursors is 1:100~1000；The titanium precursors, alcoholic solvent, acid volume ratio be 5~20:100~200:0.3~70；The molar ratio of the iron ion and titanium precursors is 0.1~5:100；By the mixture be placed in autoclave in 160~240 DEG C reaction 4~for 24 hours, after being cooled to room temperature obtain photochemical catalyst alcohol dispersion liquid；It is centrifugated the alcohol dispersion liquid, obtains the photochemical catalyst after washing and drying.G-C prepared by the present invention3N4/Fe‑TiO2Photochemical catalyst, good degradable organic pollutant effect, all has broad application prospects in fields such as water process, air cleaning and sterilizings under visible light illumination.
Description
Technical field
The present invention relates to nano-photocatalyst material technical fields, more particularly to the compound Fe2O3 doping titanium dioxide of g- carbonitride
Titanium (g-C3N4/Fe-TiO2) and preparation method thereof.
Background technique
Titanium dioxide (TiO is had found from Fujishima and Honda in 19722) on electrode the phenomenon that photodegradation water
Since (Nature, 1972,238 (5358): 37-39), Photocatalitic Technique of Semiconductor has stepped into a completely new stage.Numerous
In photochemical catalyst, TiO2Because it is stablized, nontoxic, without secondary pollution, fast light burn into photocatalytic activity is high and preparation cost is cheap etc.
Advantage, and become the photochemical catalyst that is most widely used, environmental improvement, dye-sensitized solar cells, water photodissociation hydrogen manufacturing with
And CO2The fields such as reduction play vital effect.
TiO2Main disadvantage --- forbidden bandwidth (anatase and brockite 3.2eV, rutile 3.0eV) is wide, makes it
The ultraviolet light (only accounting for 4~5% in sunlight ingredient) of 385nm can only be less than using wave-length coverage, to limit TiO2's
Large-scale application.By with other semiconductors couplings, nonmetal doping, doped transition metal ions are ion co-doped, with
And the means such as surface noble metal loading can effectively extend TiO2Spectral response range is to visible light region.However, traditional TiO2
Base visible light catalyst, as N adulterates TiO2, low, reduction that there are still quantum efficiencies caused by photo-generate electron-hole recombination rate height
The problems such as ability is low and photohole mobility is low.
g-C3N4Also known as graphite phase carbon nitride has good photocatalysis performance, and it is desirable to find one kind to meet material
Material combines the advantages of the two.
Summary of the invention
In order to overcome the deficiencies of the prior art, the present invention provides a kind of Fe2O3 doping two that visible-light response type g- carbonitride is compound
Titanium oxide (g-C3N4/Fe-TiO2) Z-type photochemical catalyst preparation method, include the following steps:
Titanium precursors, alcoholic solvent, acid and iron ion and g- carbonitride are mixed to form mixture in proportion；The g- nitridation
The mass ratio of carbon and the titanium precursors is 1:100~1000；The titanium precursors, alcoholic solvent, acid volume ratio be 5~
20:100~200:0.3~70；The iron ion and the titanium precursors molar ratio are 0.1~5:100；The concentration of the acid is
1~6mol/L.
By the mixture be placed in autoclave in 160~240 DEG C reaction 4~for 24 hours, after being cooled to room temperature obtain g- carbonitride
The alcohol dispersion liquid of compound Fe2O3 doping titanium dioxide Z-type photochemical catalyst；
It is centrifugated the alcohol dispersion liquid of the compound Fe2O3 doping titanium dioxide Z-type photochemical catalyst of the g- carbonitride, washing is dried
The compound Fe2O3 doping titanium dioxide Z-type photochemical catalyst of the g- carbonitride is obtained after dry.
Wherein, the molar ratio of the iron ion and the titanium precursors is 0.2~2:100.
Wherein, Iron source chooses at least one of ferric nitrate, iron chloride, ferric sulfate.
Wherein, it is at least one to be selected from titanium tetrachloride, butyl titanate, tetraisopropyl titanate for the titanium precursors.
Wherein, it is any to be selected from ethyl alcohol, normal propyl alcohol, isopropanol for the alcoholic solvent.
Wherein, the acid is at least one selected from hydrochloric acid, acetic acid, nitric acid, sulfuric acid, the concentration of aqueous solution of the acid for 1~
6mol/L。
The present invention also provides this Z-type photochemical catalyst, the Z-type photochemical catalyst include iron ion doping titanium dioxide and
The g- carbonitride compound with the titanium dioxide of doping.
Wherein, the molar ratio of the iron ion and the titanium dioxide is 0.1~5:100.
Wherein, the iron ion and the g- carbonitride mole-mass ratio is 0.0045~0.09mol:2~10g.
The utility model has the advantages that
(1) present invention prepares the compound Fe2O3 doping titanium dioxide (g-C of visible-light response type g- carbonitride3N4/Fe-
TiO2) Z-type photochemical catalyst, with TiO2It compares, which shows higher visible light catalysis activity, shows the photocatalysis
The Strong oxdiative reproducibility and high quantum efficiency of agent；
(2) in photochemical catalyst of the invention, iron is mixed with TiO2In lattice, photohole and electronics restrained effectively
It is compound, enhance the photocatalysis efficiency of photochemical catalyst；
(3) compared with traditional semiconductors coupling, a kind of non-metal semiconductive g-C that the present invention selects3N4Material overcomes
Heavy metal pollution caused by traditional metal semiconductor, while the simple process, save raw material and equipment
(4) g-C that the present invention is prepared by one step hydro thermal method3N4/Fe-TiO2Z-type photochemical catalyst assigns titanium dioxide
While visible light catalysis activity, also make prepared g-C3N4/Fe-TiO2Z-type photochemical catalyst is good under visible light illumination
Degradable organic pollutant effect, all has broad application prospects in fields such as water process, air cleaning and sterilizings.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1 photochemical catalyst of the embodiment of the present invention；
Fig. 2 is the infrared spectrum of 1 photochemical catalyst of the embodiment of the present invention；
Fig. 3 is electron spin resonance (ESR) figure of 1 photochemical catalyst of the embodiment of the present invention；
Fig. 4 is the efficiency for the Photocatalytic Degradation of Phenol that control experiment 1 of the present invention, control experiment 2 and embodiment 1 obtain respectively
Compare figure.
Fig. 5 is the transmission electron microscope picture of the embodiment of the present invention 1.
Fig. 6 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1.
Specific embodiment
In the following, will be described in detail to the embodiment of the present invention.
The present invention provides a kind of Fe2O3 doping titanium dioxide (g-C that visible-light response type g- carbonitride is compound3N4/Fe-TiO2)
The preparation method of Z-type photochemical catalyst, includes the following steps:
Step 1: titanium precursors, alcoholic solvent, acid and iron ion and g- carbonitride are mixed to form mixture in proportion；Institute
State titanium precursors, alcoholic solvent, acid volume ratio be 5~20:100~200:0.3~70；The iron ion and the titanium precursors
Molar ratio be 0.1~5:100.Wherein, the mass ratio of the g- carbonitride and the titanium precursors is 1:100~1000.
The titanium precursors can be at least one selected from titanium tetrachloride, butyl titanate, tetraisopropyl titanate；The alcohol is molten
It is any that agent is selected from ethyl alcohol, normal propyl alcohol, isopropanol；The acid is at least one selected from hydrochloric acid, acetic acid, nitric acid, sulfuric acid, the acid
Concentration is 1~6mol/L.
Wherein, Iron source chooses at least one of ferric nitrate, iron chloride, ferric sulfate.Guarantee iron ion and titanium precursor
The molar ratio of body is within the scope of 0.1~5:100, preferably 0.2~2:100.
Step 2: the mixture is transferred in autoclave, at a temperature of 160~240 DEG C react 4~for 24 hours.Wait react
After cooled to room temperature, obtain the alcohol dispersion liquid of the compound Fe2O3 doping titanium dioxide Z-type photochemical catalyst of g- carbonitride.
Step 3: being centrifugated the alcohol dispersion liquid of the compound Fe2O3 doping titanium dioxide Z-type photochemical catalyst of the g- carbonitride,
Successively using ethanol washing 1 time and deionized water washing 2 times, then dries in an oven, it is compound to obtain the g- carbonitride
Fe2O3 doping titanium dioxide Z-type photochemical catalyst.
The following are control experiment 1, control experiment 2, embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiments 5
Response parameter and properties of product analysis, wherein 2 to 5 products obtained therefrom performance of embodiment is similar to Example 1.
The response parameter of 1 control experiment 1 of table, control experiment 2 and Examples 1 to 5
The following are product physical and chemical performance parameters and its analysis that embodiment 1 obtains:
As shown in Figure 1, there was only the TiO of Anatase known to XRD spectrum in sample2Be 25.3 ° in the presence of, 2 θ, 37.8 °,
Peak at 48.0 °, 54.0 ° and 62.4 ° respectively corresponds (101), (004), (200), (204) and (211) crystal face of anatase,
Illustrate the TiO using hydro-thermal method preparation2Nano particle is the stronger anatase of photocatalysis performance.
As shown in connection with fig. 2, g-C3N4Compound Fe-TiO2Nano particle is in 1100-1650cm-1In wavelength band (1246,
1321,1404,1456,1561 and 1629cm-1) at have multiple peaks (Fig. 2), correspond to the flexible vibration of C-N and C=N heterocyclic compound
Dynamic characteristic peak；810cm-1The absorption peak at place is the characteristic peak of triazine；3000-3300cm-1Peak in wave band is the flexible of-NH
Vibration performance peak；In 500-700cm-1It is Ti-O and Ti-O-Ti stretching vibration characteristic peak in wavelength band, this shows composite material
In contain g-C3N4And TiO2。
As shown in figure 3, signal peak occurs at g=1.99 in the product of embodiment 1, signal peak is ferric iron substitution at this
Titanic in titanium dioxide octahedron illustrates successfully to be doped into the lattice of titanium dioxide by hydro-thermal method ferric ion.
It illustrates to be prepared for Z-type g-C by simple hydro-thermal method in conjunction with the above 3 width datagram3N4/TiO2Composite photocatalyst
Agent.
The following are the light degradation property test experiments using control experiment 1,1 Pyrogentisinic Acid of control experiment 2 and embodiment.
Initial phenol concentration is 10mg/L, liquor capacity 50ml.
Take the product of control experiment 1, control experiment 2 and embodiment 1 as photochemical catalyst, concentration 1g/L, with xenon respectively
Lamp is the light source of light-catalyzed reaction (wavelength is greater than 420nm).
1h is first adsorbed in the dark before experiment, starts illumination after reaching adsorption equilibrium, it is primary every 10min sampling, with efficient
Liquid chromatograph (HPLC) detects phenol concentration, as a result as indicated at 4.
Shown in Figure 4, for the photochemical catalyst obtained of embodiment 1 after illumination 80min, the degradation rate of phenol is 100%,
Its activity titanium dioxide granule compound better than the titania nanoparticles and g- carbonitride not mixed.
According to transmissioning electric mirror test result (Fig. 5), it is known that prepared titania nanoparticles having a size of 5~10nm, because
And there is high specific surface area, there is greater catalytic efficiency.Fig. 6 is the scanning electron microscope (SEM) photograph of the catalyst, it is seen that granular
Fe2O3 doping titanium dioxide has been combined on stratiform g- carbonitride.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
Member, under the premise of not departing from the application principle, can also make several improvements and modifications, these improvements and modifications also should be regarded as
The protection scope of the application.
Claims (7)
1. a kind of preparation method of Z-type photochemical catalyst, which comprises the steps of:
Titanium precursors, alcoholic solvent, acid and iron ion and g- carbonitride are mixed to form mixture in proportion；The g- carbonitride with
The mass ratio of the titanium precursors is 1:100 ~ 1000；The titanium precursors, alcoholic solvent, acid volume ratio be 5 ~ 20:100 ~
200:0.3~70；The molar ratio of the iron ion and the titanium precursors is 0.1 ~ 5:100；The acid is selected from hydrochloric acid, acetic acid, nitre
Acid, sulfuric acid are at least one, and the concentration of the acid is 1 ~ 6 mol/L；
The mixture is placed in 160 ~ 240 DEG C of 4 ~ 24 h of reaction in autoclave, the alcohol of photochemical catalyst is obtained after being cooled to room temperature
Dispersion liquid；
It is centrifugated the alcohol dispersion liquid of the photochemical catalyst, obtains the photochemical catalyst after washing and drying.
2. the preparation method of Z-type photochemical catalyst according to claim 1, which is characterized in that before the iron ion and the titanium
The molar ratio for driving body is 0.2 ~ 2:100.
3. the preparation method of Z-type photochemical catalyst according to claim 1, which is characterized in that the Iron source chooses nitre
At least one of sour iron, iron chloride, ferric sulfate.
4. the preparation method of Z-type photochemical catalyst according to claim 1, which is characterized in that the titanium precursors are selected from tetrachloro
It is at least one to change titanium, butyl titanate, tetraisopropyl titanate.
5. the preparation method of Z-type photochemical catalyst according to claim 1, which is characterized in that the alcoholic solvent is selected from ethyl alcohol, just
Propyl alcohol, isopropanol are any.
6. a kind of Z-type photochemical catalyst that -5 any preparation methods are prepared according to claim 1, which is characterized in that
The Z-type photochemical catalyst includes the titanium dioxide and the g- carbonitride compound with the titanium dioxide of doping of iron ion doping；Wherein,
The iron ion and the g- carbonitride mole-mass ratio is the g of 0.0045 ~ 0.09 mol:2 ~ 10.
7. Z-type photochemical catalyst according to claim 6, which is characterized in that mole of the iron ion and the titanium dioxide
Than for 0.1 ~ 5:100.
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| CN106622310A (en) * | 2016-12-08 | 2017-05-10 | 济宁学院 | Preparation method of silver phosphate-titanium dioxide composite photocatalyst |
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| CN107376968B (en) * | 2017-06-30 | 2019-08-16 | 湖南大学 | Tungstic acid/double Z shaped photochemical catalyst of carbonitride/bismuth oxide and its preparation method and application |
| WO2019021189A1 (en) * | 2017-07-27 | 2019-01-31 | Sabic Global Technologies B.V. | Methods of producing a nanocomposite heterojunction photocatalyst |
| CN107952464B (en) * | 2017-12-13 | 2020-09-11 | 大连理工大学 | Novel photocatalytic material and double-photocatalytic-electrode self-bias pollution control system |
| CN108355692A (en) * | 2018-01-22 | 2018-08-03 | 华中科技大学 | Graphite phase carbon nitride/titanic oxide nano compound material of carbon auto-dope and preparation method thereof, application |
| CN108855189A (en) * | 2018-07-05 | 2018-11-23 | 盐城工学院 | A kind of Z-type Ag6Si2O7/g-C3N4Complex light photochemical catalyst and preparation method thereof |
| CN111545185B (en) * | 2020-05-09 | 2023-04-28 | 深圳市尤佳环境科技有限公司 | Preparation method and application of photocatalyst based on ionic liquid |
| CN115430451B (en) * | 2022-08-29 | 2023-10-31 | 湖南大学 | Iron-titanium co-doped porous graphite phase carbon nitride photo-Fenton catalyst and preparation method and application thereof |
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