CN115321647A - Tubular structure TiO 2 @ foamed titanium photocatalyst, preparation method thereof and application thereof in organic wastewater treatment - Google Patents
Tubular structure TiO 2 @ foamed titanium photocatalyst, preparation method thereof and application thereof in organic wastewater treatment Download PDFInfo
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- CN115321647A CN115321647A CN202210930191.6A CN202210930191A CN115321647A CN 115321647 A CN115321647 A CN 115321647A CN 202210930191 A CN202210930191 A CN 202210930191A CN 115321647 A CN115321647 A CN 115321647A
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 70
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010936 titanium Substances 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004065 wastewater treatment Methods 0.000 title abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 64
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 64
- 239000006260 foam Substances 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002071 nanotube Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 230000001699 photocatalysis Effects 0.000 claims description 21
- 238000006731 degradation reaction Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000003628 erosive effect Effects 0.000 claims description 12
- 229940117975 chromium trioxide Drugs 0.000 claims description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012224 working solution Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- 238000005562 fading Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 33
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 10
- 239000012964 benzotriazole Substances 0.000 description 10
- 230000000593 degrading effect Effects 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 8
- 229940012189 methyl orange Drugs 0.000 description 8
- 238000002048 anodisation reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000008208 nanofoam Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a tubular TiO 2 The invention discloses a @ foam titanium photocatalyst, a preparation method thereof and application in organic wastewater treatment, wherein foam titanium is used as a matrix, step-by-step anodic oxidation is carried out in ethylene glycol solution containing ammonium fluoride and ammonium sulfate, and then the substrate is placed in a muffle furnace for heat treatment at 450 ℃ for 2h to obtain anatase type TiO with a nanotube structure and a length-diameter ratio of (20-40): 1 2 @ titanium foam photocatalyst. Supported TiO prepared according to the invention 2 Compared with other carrier type catalysts, the photocatalyst has the advantages of good binding force with a substrate, large length-diameter ratio, stronger ultraviolet response performance, high photocatalytic degradation efficiency, no pollution and low cost, avoids the recovery problem of the powder catalyst, and is suitable for application in the industrial field.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to tubular TiO capable of efficiently degrading organic wastewater 2 A @ foamed titanium photocatalyst, a preparation method thereof and application thereof in organic wastewater treatment.
Background
Degrading various organic matters in the sewage, and having important significance for improving water quality and protecting environment. TiO 2 2 The photocatalysis has great potential in degrading organic matters in wastewater, has strong catalytic oxidation capacity, can almost completely mineralize organic pollutants, and has the characteristics of low energy consumption, no toxicity and no secondary pollution.
TiO currently used 2 Most of the photocatalysts are solid powder, and the dispersion effect and the utilization rate of the photocatalysts in a solution directly influence the photocatalytic performance. Nano-sized TiO 2 2 The particles have large specific surface area and can be distributed in the solution more uniformly, thereby further improving the contact area with organic matters and promoting the photocatalytic degradation efficiency. However, in practical application, the separation process of the nano-catalyst is complex and the recycling difficulty is high.
Supported TiO compounds 2 The photocatalyst has the characteristics of easy recovery and reusability, but is also compatible with TiO 2 Compared with powder catalysts, the powder catalysts have smaller effective specific surface area (length-diameter ratio of about 4. In addition, most of the carrier-type catalysts have a problem of binding force, and catalytic active ingredients are easy to peel off from the surface of the carrier in the reaction process, so that the catalytic efficiency is obviously reduced along with the increase of the recycling times.
Disclosure of Invention
Aiming at the technical problems of the prior carrier-type catalyst, the invention aims to provide a carrier-type tubular TiO with good binding force and excellent catalytic performance 2 A @ foamed titanium photocatalyst, a preparation method thereof and application thereof in organic wastewater treatment. The inventionIn the preparation method of the catalyst, a mild organic system multi-step anodic oxidation technology is specifically involved, and TiO with a nano-tube structure with small internal stress grows on the surface of the titanium foam in situ 2 Meanwhile, the length-diameter ratio of the nano tube is increased to (20-40): 1, the catalytic activity area is increased, the catalytic performance of the carrier type catalyst is obviously improved, and the application in the industrial field is realized.
The purpose of the invention is realized by the following technical scheme:
in the preparation process of the catalyst, the foamed titanium is subjected to anodic oxidation in ammonium fluoride glycol solution, and a multi-step anodic oxidation mode is adopted to reduce TiO 2 The ammonium sulfate is added into the ammonium fluoride glycol solution to promote liquid phase mass transfer and TiO to increase the internal stress between the active layer and the substrate 2 And (4) growing the nanotubes.
Further, the tubular structure TiO 2 The preparation method of the @ foamed titanium photocatalyst comprises the following steps:
1) The foamed titanium is put in acetone for ultrasonic degreasing, then is put in a solution containing hydrofluoric acid and chromium trioxide for chemical polishing treatment for 10 to 40min at the temperature of 40 to 60 ℃, and finally is cleaned by clear water for standby;
2) Carrying out three-stage stepwise anodic electrolytic oxidation treatment on the foamed titanium treated in the step 1), wherein working solutions adopted in the three-stage stepwise anodic electrolytic oxidation treatment are consistent and are ethylene glycol solutions containing 1.5-5 wt% of ammonium fluoride, and the specific process of the three-stage stepwise anodic electrolytic oxidation treatment is as follows:
s1: in the first step of anodic electrolytic oxidation, the oxidation voltage is slowly increased to 50-70V at the speed of 0.3-5.0V/s, the oxidation time is 3-5h, and then the anode is put into an erosion liquid to fade TiO on the surface 2 A film;
s2: then, carrying out second-step anodic electrolytic oxidation, directly increasing the oxidation voltage to 50-70V for 10-14h, and then putting the titanium dioxide in an erosion liquid to remove TiO on the surface 2 A film;
s3: finally, carrying out anodic electrolytic oxidation in the third step, directly increasing the oxidation voltage to 50-70V, carrying out oxidation for 1-3h, and cleaning and drying the reacted sample by using clear water;
3) Will step withPutting the sample obtained in the step 2) into a tubular furnace, slowly heating from room temperature to 450-550 ℃, heating at a heating rate of 5-10 ℃/min for heat treatment, and then keeping the temperature for 2-4 h in an air atmosphere to obtain the TiO with the nanotube structure grown on the titanium foam 2 I.e. tubular structure of TiO 2 @ titanium foam photocatalyst.
Preferably, the aperture of the titanium foam in the step 1) is 50 to 80 μm.
Preferably, in the solution containing hydrofluoric acid and chromium trioxide in the step 1), the concentration of the hydrofluoric acid is 70 to 85ml/L, and is preferably 75ml/L. The concentration of the chromium trioxide is 60-90g/L, preferably 75g/L, and the polishing time is 20-40min.
Preferably, in step 2), the working solution further contains 1 to 3wt% of ammonium sulfate, the concentration of the ammonium sulfate is preferably 2 to 5wt%, and the concentration of the ammonium fluoride in the working solution is 2.0 to 2.5wt%.
TiO obtained in step 2) 2 The nanotube has good bonding force with the foam titanium matrix.
Preferably, in step 3), the nano-tube structure TiO is grown on the titanium foam 2 The material has an anatase structure, the pipe diameter is 80 to 120nm, the pipe length is 3 to 4um, the length-diameter ratio is (20 to 40): 1, and the material has strong ultraviolet light absorption capacity.
Preferably, the oxidation voltage of the three-stage stepwise anodic electrolytic oxidation treatment in the step 2) is kept at 60V, the first step oxidation time is 3.5 to 4 hours, the second step oxidation time is 11 to 12h, the third step oxidation time is 1 to 2h, and the temperature of the three-stage stepwise anodic electrolytic oxidation treatment is 10 to 25 ℃.
Preferably, in steps S1 and S2 of step 2), the etching solution contains HF and CrO 3 The concentration of HF in the etching solution is 70 to 85ml/L, and CrO 3 The concentration of the anode is 60 to 90g/L, and the film fading time after anodic oxidation is 20 to 30min.
Tubular TiO prepared by the invention 2 The @ foamed titanium photocatalyst has good application in catalytic degradation treatment of organic wastewater, and tubular TiO is prepared by 2 The @ foamed titanium photocatalyst is put into a photocatalysis device, and is used for carrying out catalytic degradation treatment on organic wastewater under the irradiation of ultraviolet light. The ultraviolet irradiation wavelength is 365nm, and the irradiation intensity is 5 to 50mW/cm 2 。
The scheme of the invention has the following beneficial effects:
1. the invention adopts a multi-step anodic oxidation technology, tiO 2 The titanium foam is grown in situ on the surface of the titanium foam, and not only is the arrangement regular and orderly, but also the internal stress is small, and the bonding force with a matrix is good.
2. The anodic oxidation solution adopted by the invention is the glycol solution containing ammonium fluoride and ammonium sulfate, the ammonium fluoride is adopted to replace hydrofluoric acid, the reaction system is mild, the film dissolving rate is low, and long TiO can be prepared 2 A nanotube; ammonium sulfate is added as supporting electrolyte, which is helpful for mass transfer process and further promotes the growth of the nanotube, so that the prepared TiO 2 The length-diameter ratio of the nano tube can reach 40: 1, and is improved by about 10 times compared with a sample prepared by a hydrofluoric acid aqueous solution system.
3. Tubular TiO prepared by the invention 2 The @ foam titanium photocatalyst has strong ultraviolet catalytic oxidation performance and high degradation efficiency on organic matters such as benzotriazole.
4. Examples of the invention are verified, tiO 2 The @ foam titanium photocatalyst is placed in a photocatalytic device (figure 3), the degradation efficiency of benzotriazole is stabilized at 93.7% under ultraviolet irradiation, and the degradation efficiency of methyl orange is stabilized at 87.7%. By adopting multi-stage photocatalytic treatment, the degradation rate of two organic matters can reach more than 99.9 percent. Used supported TiO 2 The photocatalyst can be recycled, and the high catalytic efficiency is kept.
Drawings
FIG. 1a shows TiO with tubular structure prepared in example 1 of the present invention 2 One of the SEM images of (A);
FIG. 1b shows TiO in tubular form prepared in example 1 of the present invention 2 Second SEM picture of (a);
FIG. 1c shows TiO in tubular form obtained in comparative example 1 of the present invention 2 SEM picture of (1);
FIG. 2 shows a TiO complex prepared in example 1 of the present invention 2 Ultraviolet-visible diffuse reflection absorption spectrogram of (1);
FIG. 3 is a view showing a photocatalytic apparatus used in an experiment for degrading organic wastewater according to example 1 of the present invention;
FIG. 4 shows TiO prepared in example 1 of the present invention 2 The efficiency chart of the nano tube/foam titanium photocatalyst for degrading benzotriazole under the irradiation of ultraviolet light;
FIG. 5 shows TiO prepared in example 1 of the present invention 2 The efficiency chart of the nano tube/foam titanium photocatalyst for degrading methyl orange under the irradiation of ultraviolet light.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
(1) The average pore diameter of the titanium foam is 60 mu m, the titanium foam is ultrasonically degreased in acetone, is put into a solution containing 75ml/L hydrofluoric acid and 75g/L chromium trioxide, is chemically polished for 20min at 50 ℃, and is finally cleaned by clear water.
(2) Step-wise anodization was performed in a solution of ethylene glycol containing 2.5% ammonium fluoride +1.5% ammonium sulfate, the first step: the oxidation voltage is slowly increased to 60V at the rate of 0.5V/s, the anodic oxidation time is 4h, and then HF + CrO is added 3 Erosion liquid (HF concentration in erosion liquid is 75ml/L, crO 3 Concentration of 75g/L, the same applies hereinafter) TiO fading 2 The film stripping time is 25min; the second step is that: the anodic oxidation voltage is directly increased to 60V, the anodic oxidation time is 12h, and then HF + CrO is used 3 The erosion liquid carries out film removal, and the film removal time is 25min; the third step: the anodic oxidation voltage is directly increased to 60V, the anodic oxidation time is 2h, and the reacted sample is washed and dried.
(3) Placing the sample in a tube furnace, slowly heating to 450 ℃ at the speed of 10 ℃/min, and preserving heat for 2h in air atmosphere to obtain TiO 2 @ foamed titanium photocatalyst (SEM images thereof are shown in fig. 1a and 1 b), and the ultraviolet-visible diffuse reflection absorption spectrum of the sample (shown in fig. 2) was measured.
TiO produced in example 1 was measured by the apparatus shown in FIG. 3 2 The photocatalytic performance of the @ foamed titanium photocatalyst sample is as follows: tiO 2 2 Area of @ foamed titanium photocatalyst is 1120cm 2 Containing 100mg/L benzotriazole and 100mg/L methylThe organic wastewater with orange concentration is introduced into a photocatalytic device (the photocatalytic device has a cylindrical structure with a diameter of 20cm and a height of 25 cm) shown in FIG. 3, and TiO is added 2 The @ foamed titanium photocatalyst is vertically inserted into wastewater in the photocatalytic device, and organic wastewater is continuously fed and discharged at the flow rate of 18 ml/min. Irradiating organic wastewater in the photocatalytic device with light (ultraviolet irradiation wavelength is 365nm, intensity is 10 mW/cm) 2 ) And measuring the concentration of the organic matters in the effluent of the photocatalytic device at the 0 moment of the degradation reaction so as to calculate the degradation rate of the organic matters.
The procedure was as described above for the TiO prepared in example 1 2 The graph of the efficiency of the nanotube/foam titanium photocatalyst in degrading benzotriazole under ultraviolet light irradiation is shown in fig. 4, and the graph of the efficiency in degrading methyl orange is shown in fig. 5. As can be seen from FIGS. 4 and 5, under the condition that organic wastewater is continuously fed in and discharged from the liquid, the degradation rate is stable after 1.5 hours, and the degradation rates of benzotriazole and methyl orange are 93.7% and 87.7% respectively.
If the organic wastewater is degraded by adopting a mode of connecting two photocatalytic devices in series, the operation conditions of each photocatalytic device are the same as the operation conditions of the two photocatalytic devices. Therefore, the removal rate of benzotriazole and methyl orange is respectively improved to 99.5 percent and 98.2 percent within 1.5 hours by adopting two-stage photocatalysis treatment.
Comparative example 1:
TiO 2 the procedure for the preparation of the @ titanium foam photocatalyst was repeated as in example 1 except that "the procedure of the step (2) was replaced with: anodizing in glycol solution containing 2.5% ammonium fluoride and 1.5% ammonium sulfate, slowly raising the oxidation voltage to 60V at the rate of 0.5V/s, and anodizing for 4h ″, thus obtaining TiO 2 @ titanium foam photocatalyst. TiO obtained in comparative example 1 2 An SEM image of a @ titanium foam photocatalyst is shown in FIG. 1 c.
TiO prepared on titanium surface in organic system 2 The biggest defects of the nano tube are poor binding force and easy peeling after heat treatment. FIG. 1c shows TiO prepared by one step anodization of comparative example 1 2 Surface topography, tiO 2 The nanotube is loose and messy and is easy to occurLodging and peeling from the matrix, and the performance of the catalyst is poor in application performance.
TiO prepared by step-by-step anodic oxidation in example 1 of the present invention 2 Surface topography, see FIG. 1a, tiO 2 The nano-tubes are arranged regularly, and TiO finally grows as a result of multi-step oxidation-film stripping procedures 2 The stress of the film layer is small, and the TiO content is greatly improved 2 The bonding force between the nanotube and the matrix can be well applied to industry.
Example 2
(1) The average pore diameter of the titanium foam is 60 mu m, the titanium foam is ultrasonically degreased in acetone, the titanium foam is put into a solution containing 75ml/L hydrofluoric acid and 75g/L chromium trioxide, chemical polishing treatment is carried out for 20min at 50 ℃, and the titanium foam is cleaned.
(2) Step-wise anodization was carried out in a solution of 2.5% ammonium fluoride in ethylene glycol, the first step: the oxidation voltage is slowly increased to 60V at the rate of 0.5V/s, the anodic oxidation time is 4h, and then HF + CrO 3 Erosion liquid (HF concentration in erosion liquid is 75ml/L, crO 3 Concentration of 75g/L, the same applies hereinafter) TiO fading 2 The film stripping time is 25min; the second step is that: the anodic oxidation voltage is directly increased to 60V, the anodic oxidation time is 12h, and then HF + CrO is used 3 The film is removed by the erosion liquid for 25min; the third step: the anodic oxidation voltage is directly increased to 60V, the anodic oxidation time is 2h, and the reacted sample is washed and dried.
(3) Placing the sample in a tube furnace, slowly heating to 450 ℃ at the speed of 10 ℃/min, and preserving heat for 2h in air atmosphere to obtain TiO 2 @ titanium foam photocatalyst.
(4) TiO 2 obtained in example 2 was measured by using an apparatus shown in FIG. 3 2 The photocatalytic performance of the @ foam titanium photocatalyst sample, the test conditions were repeated in example 1, and the experimental results were: the degradation rates of benzotriazole and methyl orange are respectively 90.3% and 82.4%.
Example 3
(1) The average pore diameter of the titanium foam is 60 mu m, the titanium foam is ultrasonically degreased in acetone, the titanium foam is put into a solution containing 75ml/L hydrofluoric acid and 75g/L chromium trioxide, chemical polishing treatment is carried out for 20min at 50 ℃, and the titanium foam is cleaned.
(2) Step-wise anodization was performed in a solution of ethylene glycol containing 2.5% ammonium fluoride +1.5% ammonium sulfate, the first step: the oxidation voltage is slowly increased to 60V at the rate of 0.5V/s, the anodic oxidation time is 4h, and then HF + CrO 3 The etching solution (the concentration of HF in the etching solution is 75ml/L, crO) 3 Concentration of 75g/L, the same applies below) for TiO fading 2 The film stripping time is 25min; the second step is that: the anodic oxidation voltage is directly increased to 60V, the anodic oxidation time is 12h, and then HF + CrO is added 3 The erosion liquid carries out film removal, and the film removal time is 25min; the third step: the anodic oxidation voltage is directly increased to 60V, the anodic oxidation time is 2h, and the reacted sample is washed and dried.
(3) Placing the sample in a tube furnace, slowly heating to 550 ℃ at the speed of 10 ℃/min, and preserving heat for 2h in air atmosphere to obtain TiO 2 @ titanium foam photocatalyst.
(4) TiO 2 obtained in example 3 was measured by using an apparatus shown in FIG. 3 2 The photocatalytic performance of the @ foam titanium photocatalyst sample, the test conditions were repeated in example 1, and the experimental results were: the degradation rates of benzotriazole and methyl orange are respectively 90.6% and 85.2%.
Example 4
(1) The average pore diameter of the titanium foam is 60 mu m, the titanium foam is ultrasonically degreased in acetone, the titanium foam is put into a solution containing 75ml/L hydrofluoric acid and 75g/L chromium trioxide, chemical polishing treatment is carried out for 20min at 50 ℃, and the titanium foam is cleaned.
(2) Anodizing in 0.5% hydrofluoric acid solution at 20V for 20min, and washing and drying the reacted sample.
(3) Placing the sample in a tube furnace, slowly heating to 450 ℃ at the speed of 10 ℃/min, and preserving heat for 2h in air atmosphere to obtain TiO 2 @ titanium foam photocatalyst.
(4) TiO 2 obtained in example 4 was measured by using an apparatus shown in FIG. 3 2 The photocatalytic performance of the @ foam titanium photocatalyst sample, the test conditions were repeated in example 1, and the experimental results were: the degradation rates of benzotriazole and methyl orange are respectively84.1% and 76.5%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. Tubular structure TiO 2 The preparation method of the @ foamed titanium photocatalyst is characterized by comprising the following steps of:
1) Sequentially carrying out oil removal and chemical polishing on the foamed titanium for later use;
2) Carrying out three-stage stepwise anodic electrolytic oxidation treatment on the foamed titanium treated in the step 1), wherein working solutions adopted in the three-stage stepwise anodic electrolytic oxidation treatment are consistent and are ethylene glycol solutions containing 1.5-5 wt% of ammonium fluoride, and the specific process of the three-stage stepwise anodic electrolytic oxidation treatment is as follows:
s1: in the first step of anodic electrolytic oxidation, the oxidation voltage is slowly increased to 50-70V at the speed of 0.3-5.0V/s, the oxidation time is 3-5h, and then the anode is put into an erosion liquid to fade TiO on the surface 2 A film;
s2: then, carrying out anodic electrolytic oxidation in the second step, directly increasing the oxidation voltage to 50-70V for 10-14h, and then putting the anode into an erosion liquid to remove TiO on the surface 2 A film;
s3: finally, carrying out anodic electrolytic oxidation in the third step, directly increasing the oxidation voltage to 50-70V, wherein the oxidation time is 1-3h, and cleaning and drying the reacted sample by using clean water;
3) Placing the sample obtained in the step 2) in a tubular furnace, slowly heating from room temperature to 450-550 ℃, heating at a heating rate of 5-10 ℃/min for heat treatment, and then keeping the temperature for 2-4 h in an air atmosphere to obtain the TiO with the nanotube structure grown on the titanium foam 2 I.e. tubular structure TiO 2 @ titanium foam photocatalyst.
2. The tubular TiO of claim 1 2 The preparation method of the @ titanium foam photocatalyst is characterized in that the aperture of titanium foam in the step 1) is 50-80 microns, the titanium foam is placed in acetone for ultrasonic degreasing, and then a solution containing hydrofluoric acid and chromium trioxide is placed in the acetonePerforming chemical polishing treatment at 40-60 ℃ for 10-40min, and finally cleaning with clear water; in the solution containing hydrofluoric acid and chromium trioxide, the concentration of the hydrofluoric acid is 70-85ml/L, and the concentration of the chromium trioxide is 60-90g/L.
3. The tubular TiO of claim 1 2 The preparation method of the @ foamed titanium photocatalyst is characterized in that in the step 2), the oxidation voltage of three-stage stepwise anodic electrolytic oxidation treatment is kept at 60V, the first-stage oxidation time is 3.5-4h, the second-stage oxidation time is 11-12h, the third-stage oxidation time is 1-2h, and the temperature of the three-stage stepwise anodic electrolytic oxidation treatment is 10-25 ℃.
4. The tubular TiO of claim 1 2 The preparation method of the @ foamed titanium photocatalyst is characterized in that in the step 2), the working solution further contains 1-3wt% of ammonium sulfate, the concentration of the ammonium sulfate is preferably 2-5wt%, and the concentration of ammonium fluoride in the working solution is 2.0-2.5wt%.
5. The tubular TiO of claim 1 2 The preparation method of the @ foamed titanium photocatalyst is characterized in that in the step 2), the erosion liquid contains HF and CrO 3 The concentration of HF in the etching solution is 70 to 85ml/L, and CrO 3 The concentration of the anode is 60 to 90g/L, and the film fading time after anodic oxidation is 20 to 30min.
6. The tubular TiO of claim 1 2 The preparation method of the @ titanium foam photocatalyst is characterized in that in the step 3), tiO with a nanotube structure is grown on the titanium foam 2 The material has an anatase structure, the pipe diameter is 80 to 120nm, the pipe length is 3 to 4um, the length-diameter ratio is (20 to 40): 1, and the material has strong ultraviolet light absorption capacity.
7. TiO with tubular structure prepared by the method of any one of claims 1 to 6 2 @ titanium foam photocatalyst.
8. As in claimThe tubular TiO of claim 7 2 The application of the @ foamed titanium photocatalyst in catalytic degradation treatment of organic wastewater.
9. The method of claim 8, wherein the tubular structure is TiO-doped 2 The @ foamed titanium photocatalyst is put into a photocatalysis device, and is used for carrying out catalytic degradation treatment on organic wastewater under the irradiation of ultraviolet light.
10. The use as claimed in claim 9, wherein the UV radiation has a wavelength of 365nm and an intensity of 5 to 50mW/cm 2 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653728A (en) * | 2009-09-04 | 2010-02-24 | 大连理工大学 | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst |
| CN108360040A (en) * | 2018-03-05 | 2018-08-03 | 中北大学 | There is the preparation method of light thermal property porous yarn for accelerating water evaporation |
| CN108585106A (en) * | 2018-05-17 | 2018-09-28 | 同济大学 | A method of the selective photocatalysis oxidation removal nonyl phenol based on hydrophobic effect |
| CN110240232A (en) * | 2019-05-24 | 2019-09-17 | 同济大学 | A kind of photoelectrocatalysioxidization oxidization method of efficient removal Atrazine |
| CN114068202A (en) * | 2021-11-23 | 2022-02-18 | 东北石油大学 | Titanium dioxide nanotube photoelectric capacity material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653728A (en) * | 2009-09-04 | 2010-02-24 | 大连理工大学 | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst |
| CN108360040A (en) * | 2018-03-05 | 2018-08-03 | 中北大学 | There is the preparation method of light thermal property porous yarn for accelerating water evaporation |
| CN108585106A (en) * | 2018-05-17 | 2018-09-28 | 同济大学 | A method of the selective photocatalysis oxidation removal nonyl phenol based on hydrophobic effect |
| CN110240232A (en) * | 2019-05-24 | 2019-09-17 | 同济大学 | A kind of photoelectrocatalysioxidization oxidization method of efficient removal Atrazine |
| CN114068202A (en) * | 2021-11-23 | 2022-02-18 | 东北石油大学 | Titanium dioxide nanotube photoelectric capacity material and preparation method and application thereof |
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