CN105536820A - Method for preparing visible-light-active TiO2/Cu2S composite photocatalyst for removing Cr from water - Google Patents
Method for preparing visible-light-active TiO2/Cu2S composite photocatalyst for removing Cr from water Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 27
- 230000000694 effects Effects 0.000 claims abstract description 26
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003607 modifier Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- 230000003301 hydrolyzing effect Effects 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000643 oven drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000008235 industrial water Substances 0.000 abstract description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 7
- 239000002114 nanocomposite Substances 0.000 description 7
- 238000005034 decoration Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a method for preparing a visible-light-active TiO2/Cu2S composite photocatalyst for removing Cr from water. According to the method, the TiO2/Cu2S composite photocatalyst with high visible-light activity is prepared by adopting an ultrasonic assisted solvothermal method in a manner of taking titanium tetrachloride as a titanium source and taking cuprous sulfide as a composite modifier. During experimentation, a feasible and effective anti-coating coupling method is adopted and is assisted by an ultrasonic stripping means, so that the structural stability of the composite catalyst is guaranteed, and meanwhile, the composite catalyst can have relatively high photocatalytic activity to Cr(VI). The obtained TiO2/Cu2S composite photocatalyst can be used for reducing a heavy metal Cr (VI) in the water into Cr (III), then, Cr (III) is converted into insoluble Cr(OH)3 which is attached to the surface of the catalyst, and thus, the aim of thoroughly purifying the water is achieved, so that the composite photocatalyst has a broad application prospect in the removal of similar heavy-metal pollutants from industrial water.
Description
Technical field
The present invention relates to the preparation field of visible light activity nano composite material, being specifically related to the TiO of the visible light activity for removing Cr in water body
2/ Cu
2the preparation method of S composite photo-catalyst.
Background technology
Water pollution problems is day by day serious, and water environmental problems more and more receives publicity and attention.Heavy metal in industrial wastewater is one of main water pollutant, wherein Cr (VI) has high toxicity and carcinogenicity, and how effectively Cr (VI) to be converted into Cr (III) becomes the important means of administering Cr (VI) and polluting.Traditional administering method has certain limitation, and Photocatalitic Technique of Semiconductor is subject to extensive concern as a kind of new method in process water pollutant.Wherein, nano-TiO
2there is the advantages such as good photocatalysis performance, high stability, corrosion resistance, nontoxicity, low cost, in the Environment control such as wastewater treatment, purification of air, antibiotic and sterilizing, all show its outstanding performance, be thus considered to one of the most promising green light catalyst.But due to TiO
2self there are some defects as poor in visible light activity, light induced electron/hole-recombination probability is high, seriously limits the application of its reality.
Cuprous sulfide (Cu
2s) in recent years progressively come into one's own as the effective photosensitizer of one and study.Block cuprous sulfide itself there is no photocatalytic activity, and this is mainly because block cuprous sulfide band gap is narrower, and photo-generate electron-hole is higher to recombination probability.But when cuprous sulfide is in nano-scale, because energy level uprises, band gap broadens, impel effective separation that photo-generate electron-hole is right, make cuprous sulfide have good photocatalytic activity.This method makes full use of this advantage of cuprous sulfide, and auxiliary with ultrasonic stripping, achieves TiO under hydro-thermal polymerization and anti-coating decoration triple role
2with Cu
2compound between S, gained composite catalyst has better clearance to Cr (VI), and it is simple that this method has technique, and cost is lower, and operation controllable operating performance is good, can be widely used in the preparation of visible light activity nano composite material.
Plant etc. (IlanJen-LaPlante, AyeletTeitelboim, IddoPinkas.J.Phys.Chem.Lett.2014,5,590) adopt base exchange method to obtain the CdS-Cu of nanorod structure
2s nano composite material, gained composite has better photocatalytic activity to methyl blue, and CdS-Cu
2the photocatalytic activity of S nano composite material and Cu
2the content of S has close relationship.Kim etc. (YunheeKim, KeeYoungPark, DongMyungJang.J.Phys.Chem.C2010,114,22141) adopt the hot growth method of simple situ solvent to obtain Au-Cu
2s core-shell structure copolymer nano hybridization structure, research process finds that Au is nanocrystalline and is embedded into Cu as nuclear structure
2the transmission of light induced electron at catalyst interface effectively can be improved in the inside of S, and then improves composite catalyst to the photocatalytic degradation capability of dyestuff.Wang etc. (HuanWang, LiLiu, YafeiWang.MaterialsLetters, 2015,160,351) utilize Cu
2s removes to modify the Bi with three-dimensional structure
2wO
6flower-like nanostructure, thus obtain the Cu with high visible-light activity
2s/Bi
2wO
6nano composite material, by showing the degradation experiment of rhdamine B, works as Cu
2when the mass fraction of S is 9%, catalyst can reach 96% to the degradation efficiency of rhodamine B.
Summary of the invention
The invention provides a kind of TiO of the visible light activity for removing Cr in water body
2/ Cu
2the preparation method of S composite photo-catalyst.The method is with titanium tetrachloride (TiCl
4) be titanium source, cuprous sulfide (Cu
2s) be composite modifier, adopt comparatively easy ultrasonic wave added solvent-thermal method to obtain the TiO with high visible-light activity
2/ Cu
2s composite photo-catalyst.This method makes full use of this advantage of cuprous sulfide, and auxiliary with ultrasonic stripping, achieves TiO under hydro-thermal polymerization and anti-coating decoration triple role
2with Cu
2compound between S, gained composite catalyst reaches the object of thoroughly purification to Cr in water body (VI), and it is simple that this method has technique, and cost is lower, and operation controllable operating performance is good, can be widely used in the preparation of visible light activity nano composite material.
Object of the present invention can be realized by following scheme.
For removing the TiO of the visible light activity of Cr in water body
2/ Cu
2the preparation method of S composite photo-catalyst, the method selects titanium tetrachloride (TiCl
4) be titanium source, cuprous sulfide (Cu
2s) be composite modifier, adopt ultrasonic wave added sol-gel solvent-thermal method to obtain the TiO with visible light activity
2/ Cu
2s composite photo-catalyst, concrete preparation process is as follows:
(1) titanium tetrachloride ethanolic solution 20mL is prepared in beaker;
(2) according to Cu
2tiO after S and titanium tetrachloride hydrolysis
2mol ratio be (0.002 ~ 0.2): 1 adds Cu in the beaker of step (1)
2s, is placed in the ultrasonic process 40 ~ 120min of ultrasonic washing instrument, obtains dispersion liquid by beaker;
(3) in the dispersion liquid of step (2) gained, progressively drip hydrolytic reagent 4mL, continue ultrasonic process 5 ~ 10min to promote the hydrolysis of titanium tetrachloride; Described hydrolytic reagent is the mixed solution of calgon, glycerine and ethanol;
(4) be transferred in polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle by step (3) products therefrom, and be placed in air dry oven, set temperature is 140 ~ 180 DEG C of heat treatment 3 ~ 5h, naturally cools to room temperature after heat treatment;
(5) deionized water and absolute ethyl alcohol is adopted to wash respectively step (4) products therefrom, after, product is placed in air dry oven drying process 3 ~ 5h, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.
Further, in step (1), the concentration of reaction medium titanium tetrachloride ethanolic solution is 0.15 ~ 0.45mol/L.
Further, the Cu adopted in step (2)
2s is technical grade, is inorganic sensitized dose, and mass percent is 80%.
Further, each component of step (3) described hydrolytic reagent accounts for the percentage of hydrolytic reagent quality and is: calgon 0.1 ~ 0.4%; Glycerine 0.02 ~ 0.2%; Ethanol 0.4 ~ 1.0%; In hydrolytic reagent, all the other components are water.
Further, step (2) and step (3) are carried out under room temperature 25 DEG C of conditions.
Further, the volume of step (1) described beaker is 100mL.
Further, the volume of the described polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of step (4) is 25mL.
Further, the temperature of step (5) described air dry oven is 80 DEG C.
The present invention has following advantage and effect relative to prior art:
(1) the present invention makes full use of cuprous sulfide and titanium dioxide two kinds of semi-conducting materials advantage separately, adopts triple complex method to comprise ultrasonic stripping broken, achieves TiO under hydro-thermal polymerization and anti-coating decoration
2nano particle covered composite yarn Cu
2s, thus form the TiO with better stability and photocatalytic activity
2/ Cu
2s composite photo-catalyst, this method has the advantages such as technique is simple, cost is lower, it is controlled to operate, good operation performance, can be widely used in the preparation of visible light activity nano composite material.
(2) gained TiO of the present invention
2/ Cu
2s composite photo-catalyst, can realize the object that in water body, Cr (VI) thoroughly removes under the effect of visible ray, this removal for the similar heavy metal contaminants of industrial water body has certain application prospect.
Accompanying drawing explanation
Fig. 1 is the TiO that the embodiment of the present invention 1 obtains
2/ Cu
2the SEM figure of S composite photo-catalyst.
Fig. 2 is the TiO that the embodiment of the present invention 1 obtains
2/ Cu
2the EDS figure of S composite photo-catalyst.
The TiO that Fig. 3 obtains for the embodiment of the present invention 2
2/ Cu
2s composite photo-catalyst is to containing in Cr (VI) aqueous solution processing procedure, and the absorbance curve of Cr (VI) is with the variation diagram of light application time.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, it should be noted that, embodiment does not form the restriction to application claims protection domain.
Embodiment 1
Preparation 0.45mol/L titanium tetrachloride ethanolic solution 20mL in the beaker of 100mL, according to Cu after titanium tetrachloride hydrolysis
2s:TiO
2mol ratio is 0.008:1, adds the technical grade Cu that mass percent is 80% in beaker
2s; Beaker is placed in ultrasonic washing instrument ultrasonic process 60min.Then, in the dispersion liquid of gained, progressively instilling 4mL hydrolytic reagent, (percentage that each component of hydrolytic reagent accounts for hydrolytic reagent quality is: calgon 0.4%, glycerine 0.2%, ethanol 1%, all the other components are water), continue ultrasonic process 10min to promote titanium tetrachloride (TiCl
4) hydrolysis, products therefrom is transferred in the polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of 25mL, and to be placed in temperature be heat treatment 3h in 140 DEG C of air dry ovens, after heat treatment, naturally cool to room temperature.Deionized water and absolute ethyl alcohol is finally adopted by hydrothermal product to wash respectively, after, product is placed in 80 DEG C of air dry oven drying process 5h, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.Gained TiO
2/ Cu
2microcellular structure surperficial in S composite photo-catalyst and projection distribute uniformly, and the absorption of the Cr that is highly advantageous to (VI) and reduction, the results are shown in Figure 1.TiO
2/ Cu
2the EDAX results of S composite photo-catalyst shows, containing elements such as Cu, S, Ti and O in composite catalyst, TiO is described
2with Cu
2s defines certain composite construction with some form, the results are shown in Figure 2.
Embodiment 2
Preparation 0.4mol/L titanium tetrachloride ethanolic solution 20mL in the beaker of 100mL, according to Cu after titanium tetrachloride hydrolysis
2s:TiO
2mol ratio is 0.02:1, adds the technical grade Cu that mass percent is 80% in beaker
2s; Beaker is placed in ultrasonic washing instrument ultrasonic process 60min.Then, in the dispersion liquid of gained, progressively instilling 4mL hydrolytic reagent, (percentage that each component of hydrolytic reagent accounts for hydrolytic reagent quality is: calgon 0.4%, glycerine 0.2%, ethanol 1%, all the other components are water), continue ultrasonic process 10min to promote titanium tetrachloride (TiCl
4) hydrolysis, products therefrom is transferred in the polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of 25mL, and to be placed in temperature be heat treatment time 3h in 180 DEG C of air dry ovens, after heat treatment, naturally cool to room temperature.Finally, deionized water and absolute ethyl alcohol is adopted by hydrothermal product to wash respectively, after, product is placed in the air dry oven drying process 5h of 80 DEG C, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.As shown in Figure 3, in 60min light application time, TiO
2/ Cu
2the Cr (VI) in water body almost removed completely by S composite catalyst, the absorbance peak value of Cr (III) is also along with the prolongation of light application time is close to disappearance simultaneously, this is mainly due under visible ray effect, Cr (VI) in water body is first reduced to Cr (III) by composite catalyst, and Cr (III) is then with insoluble Cr (OH)
3form exist, and be attached to catalyst surface, settle down with catalyst.This illustrates the TiO adopting this method to obtain
2/ Cu
2s composite photo-catalyst thoroughly can remove the Cr (VI and III) in water body, and then reaches the purification object thoroughly of water body.
Embodiment 3
Preparation 0.4mol/L titanium tetrachloride ethanolic solution 20mL in the beaker of 100mL, according to Cu after titanium tetrachloride hydrolysis
2s:TiO
2mol ratio is 0.02:1, adds the technical grade Cu that mass percent is 80% in beaker
2s; Beaker is placed in ultrasonic washing instrument ultrasonic process 60min.Then, in the dispersion liquid of gained, being progressively added dropwise to 4mL hydrolytic reagent, (percentage that each component of hydrolytic reagent accounts for hydrolytic reagent quality is: calgon 0.4%, glycerine 0.2%, ethanol 1%, all the other components are water), continue ultrasonic process 10min to promote titanium tetrachloride (TiCl
4) hydrolysis, products therefrom is transferred in the polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of 25mL, and to be placed in temperature be heat treatment time 3h in the air dry oven of 140 DEG C, after heat treatment, naturally cool to room temperature.Finally, deionized water and absolute ethyl alcohol is adopted by hydrothermal product to wash respectively, after, product is placed in the air dry oven drying process 5h of 80 DEG C, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.Under visible ray effect, work as TiO
2/ Cu
2when the consumption of S composite photo-catalyst is 0.8g/L, light application time is 60min, is 93.7% to the clearance of Cr (VI); When the consumption of catalyst is 1.0g/L, when light application time is 90min, can 100% be reached to the clearance of Cr (VI).
Embodiment 4
Preparation 0.15mol/L titanium tetrachloride ethanolic solution 20mL in the beaker of 100mL, according to Cu after titanium tetrachloride hydrolysis
2s:TiO
2mol ratio is 0.2:1, adds the technical grade Cu that mass percent is 80% in beaker
2s; Beaker is placed in ultrasonic washing instrument ultrasonic process 60min.Then, in the dispersion liquid of gained, progressively instilling 4mL hydrolytic reagent, (percentage that each component of hydrolytic reagent accounts for hydrolytic reagent quality is: calgon 0.4%, glycerine 0.2%, ethanol 1%, all the other components are water), continue ultrasonic process 10min to promote titanium tetrachloride (TiCl
4) hydrolysis, products therefrom is transferred in the polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of 25mL, and to be placed in temperature be heat treatment 3h in 140 DEG C of air dry ovens, after heat treatment, naturally cool to room temperature.Deionized water and absolute ethyl alcohol is finally adopted by hydrothermal product to wash respectively, after, product is placed in 80 DEG C of air dry oven drying process 5h, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.Gained TiO
2/ Cu
2s composite photo-catalyst can reach more than 97% to Cr (VI) clearance.
Embodiment 5
Preparation 0.4mol/L titanium tetrachloride ethanolic solution 20mL in the beaker of 100mL, according to Cu after titanium tetrachloride hydrolysis
2s:TiO
2mol ratio is 0.002:1, adds the technical grade Cu that mass percent is 80% in beaker
2s; Beaker is placed in ultrasonic washing instrument ultrasonic process 60min.Then, in the dispersion liquid of gained, progressively instilling 4mL hydrolytic reagent, (percentage that each component of hydrolytic reagent accounts for hydrolytic reagent quality is: calgon 0.4%, glycerine 0.2%, ethanol 1%, all the other components are water), continue ultrasonic process 10min to promote titanium tetrachloride (TiCl
4) hydrolysis, products therefrom is transferred in the polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of 25mL, and to be placed in temperature be heat treatment 3h in 140 DEG C of air dry ovens, after heat treatment, naturally cool to room temperature.Deionized water and absolute ethyl alcohol is finally adopted by hydrothermal product to wash respectively, after, product is placed in 80 DEG C of air dry oven drying process 5h, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.Gained TiO
2/ Cu
2s composite photo-catalyst can reach more than 94% to Cr (VI) clearance.
Claims (8)
1. for removing the TiO of the visible light activity of Cr in water body
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, the method selects titanium tetrachloride to be titanium source, and cuprous sulfide is composite modifier, adopts ultrasonic wave added sol-gel solvent-thermal method to obtain the TiO with visible light activity
2/ Cu
2s composite photo-catalyst, concrete preparation process is as follows:
(1) titanium tetrachloride ethanolic solution 20mL is prepared in beaker;
(2) according to Cu
2tiO after S and titanium tetrachloride hydrolysis
2mol ratio be (0.002 ~ 0.2): 1 adds Cu in the beaker of step (1)
2s, is placed in the ultrasonic process 40 ~ 120min of ultrasonic washing instrument, obtains dispersion liquid by beaker;
(3) in the dispersion liquid of step (2) gained, progressively drip hydrolytic reagent 4mL, continue ultrasonic process 5 ~ 10min to promote the hydrolysis of titanium tetrachloride; Described hydrolytic reagent is the mixed solution of calgon, glycerine and ethanol;
(4) be transferred in polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle by step (3) products therefrom, and be placed in air dry oven, set temperature is 140 ~ 180 DEG C of heat treatment 3 ~ 5h, naturally cools to room temperature after heat treatment;
(5) deionized water and absolute ethyl alcohol is adopted to wash respectively step (4) products therefrom, after, product is placed in air dry oven drying process 3 ~ 5h, simple grinding can obtain TiO
2/ Cu
2s composite photo-catalyst.
2. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, in step (1), the concentration of reaction medium titanium tetrachloride ethanolic solution is 0.15 ~ 0.45mol/L.
3. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, the Cu adopted in step (2)
2s is technical grade, and mass percent is 80%.
4. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, the percentage that each component of step (3) described hydrolytic reagent accounts for hydrolytic reagent quality is: calgon 0.1 ~ 0.4%; Glycerine 0.02 ~ 0.2%; Ethanol 0.4 ~ 1.0%; In hydrolytic reagent, all the other components are water.
5. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, step (2) and step (3) are all carried out under room temperature 25 DEG C of conditions.
6. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, the volume of step (1) described beaker is 100mL.
7. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, the volume of the described polytetrafluoroethylsubstrate substrate hydrothermal reaction kettle of step (4) is 25mL.
8. the TiO of the visible light activity for removing Cr in water body according to claim 1
2/ Cu
2the preparation method of S composite photo-catalyst, is characterized in that, the temperature of step (5) described air dry oven is 80 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105944763A (en) * | 2016-05-17 | 2016-09-21 | 南京工业大学 | Cuprous selenide cluster supported visible light photocatalyst with property of reducing Cr (VI) ions |
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| CN110013863A (en) * | 2019-03-26 | 2019-07-16 | 桂林理工大学 | One step solvent-thermal process CuS-WO of one kind3The preparation method of composite material |
| CN110013863B (en) * | 2019-03-26 | 2021-11-16 | 桂林理工大学 | One-step solvothermal synthesis of CuS-WO3Method for preparing composite material |
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