CN117682628A - Method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode - Google Patents
Method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode Download PDFInfo
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- CN117682628A CN117682628A CN202311680781.9A CN202311680781A CN117682628A CN 117682628 A CN117682628 A CN 117682628A CN 202311680781 A CN202311680781 A CN 202311680781A CN 117682628 A CN117682628 A CN 117682628A
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- hexavalent chromium
- bisphenol
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 124
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 20
- 239000010865 sewage Substances 0.000 title claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000002195 synergetic effect Effects 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 239000002096 quantum dot Substances 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 239000002073 nanorod Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 18
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- 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 12
- 239000003344 environmental pollutant Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 231100000719 pollutant Toxicity 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
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- 230000031700 light absorption Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
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- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- -1 polytetrafluoroethylene Polymers 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
Abstract
The invention relates to a method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode, which uses 3D BQD@TiO 2 The photoelectric electrode is a working electrode, 3D TiO 2 A three-electrode system is constructed by taking a saturated calomel electrode as a reference electrode, a water body to be treated containing bisphenol A, hexavalent chromium and sodium sulfate is taken as an electrolyte solution, and under the irradiation of a light source, bias voltage is applied to remove the bisphenol A and the hexavalent chromium in the water body to be treated by photoelectrocatalysis. The invention can realize the synergistic removal of bisphenol A (BPA) and hexavalent chromium (Cr (VI)) composite pollution in water and simulate too much100% removal of BPA and Cr (VI) is realized within 30min in sunlight, and after 5 times of circulation, the removal rates of BPA and Cr (VI) are still respectively maintained at 99.1% and 95.6%, so that the high-efficiency and stable photoelectrocatalytic oxidation-reduction performance is realized.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and relates to a method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on a titanium dioxide composite photoelectrode.
Background
At present, the technology for removing BPA in water mainly comprises a biodegradation method, a physical adsorption method and a chemical oxidation method. Although the above techniques have achieved certain effects, the problems of long time consumption, easy secondary pollution and the like are faced. More importantly, BPA in wastewater is removed by oxidative mineralization, cr (VI) reduces toxicity by reduction to Cr (III), a trace element essential to microorganisms, and two different removal principles greatly increase the complexity and difficulty of synchronous treatment. In recent decades, advanced oxidation technologies including photocatalysis and photoelectrocatalysis technologies are rapidly developed, and the method has high-efficiency reaction rate and mild experimental conditions by generating active oxygen species, and becomes one of promising water body restoration methods. Studies using photocatalytic simultaneous removal of BPA and Cr (VI) have reported that oxidation and reduction reactions are driven by photo-generated electrons and holes generated on the catalyst surface, respectively. Although the photocatalysis technology achieves a certain effect, the photocatalytic technology is limited by the form of powder materials, photo-generated electrons and holes are gathered on the surface of the same structure, and the charge separation lacks directionality, so that the oxidation-reduction efficiency is greatly influenced. And the problems of catalyst regeneration and recovery have not been solved effectively. Compared with photocatalysis, the photocatalysis technology can rapidly and thoroughly separate photo-generated electrons and holes by combining the action of an external electric field, and the efficiency of the photocatalysis reaction is remarkably improved. And the anode space and the cathode space in the photoelectric reaction system are independent, so that more favorable conditions are provided for efficient and synergistic removal of BPA through anode efficient oxidation mineralization and Cr (VI) through cathode efficient reduction elimination. Meanwhile, the photoelectrode material can be recycled through treatment, so that the use cost is greatly reduced. At present, few researches on the photoelectrocatalysis for synchronously removing BPA and Cr (VI) are reported, the focus is focused on the development of anode materials, and cathode materials are mostly carbon cloth, carbon felt or metal titanium plates, and the co-development of cathode and anode electrode materials is not yet started. Therefore, the simultaneous obtaining of cathode and anode materials with excellent photoelectrocatalytic activity is a key to achieving efficient simultaneous removal of BPA and Cr (VI).
With TiO 2 The typical semiconductor photocatalyst has the advantages of high activity, low cost, stable physical and chemical properties, no toxicity and the like, and is commonly used for degrading organic pollutants, but TiO 2 The electron transfer efficiency is low, the electron-hole recombination rate is high, and the large-scale application of the polymer is limited. In the last decade, people have often accelerated TiO by structural and interfacial engineering 2 Reducing electron-hole recombination rates such as metal/non-metal doping, defect structure, noble metal modification, and semiconductor coupling. The preparation process of the titanium dioxide photoelectrode with three-dimensional crystal plane junction property and the preparation and the application thereof are disclosed in the patent CN202110178404.X, wherein the photoelectrode is prepared by the following steps: titanium mesh is used as a titanium source, hydrochloric acid is used as a morphology control agent, hydrogen peroxide is used as an oxidant, and one-dimensional vertical rutile TiO with exposed top {111} crystal faces grows in situ on a titanium mesh substrate through a gas phase hydrothermal method 2 A nanorod; then the {101}, 111} nanocones are grown outside the nanorods through secondary hydrothermal reaction to form a three-dimensional crystal face structure, namely FH- {111} TiO 2 Ti target electrode. The patent electrode has higher performance of photodegradation of single bisphenol A, however, tiO 2 Itself is still limited by the problem of limited light response range.
Disclosure of Invention
The invention aims to provide a method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on a titanium dioxide composite photoelectrode, which can remarkably improve light absorption efficiency and charge separation and transfer capacity and realize efficient cooperative oxidation removal of bisphenol A and hexavalent chromium pollutants in water.
The aim of the invention can be achieved by the following technical scheme:
method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode, which uses 3DBQD@TiO 2 The photoelectrode is a photo anode and 3D TiO 2 A three-electrode system is constructed by taking a saturated calomel electrode as a reference electrode, a water body to be treated containing bisphenol A and/or hexavalent chromium as a treatment object, and under the irradiation of a light source such as a xenon lamp, bias voltage is applied to remove the bisphenol A and the hexavalent chromium in the water body to be treated by photoelectrocatalysis。
Further, the 3D TiO 2 The preparation process of (2) is as follows:
pretreating a metal titanium mesh, placing the pretreated metal titanium mesh in a mixed solution of hydrochloric acid, hydrogen peroxide and water, and performing gas-phase hydrothermal reaction to obtain rutile TiO 2 The volume ratio of hydrochloric acid, hydrogen peroxide and water is (4.2-5.3): 1:17, the mass fraction of hydrochloric acid is 36-38%, and the mass fraction of hydrogen peroxide is 30%.
More preferably, the specific process of pretreatment of the titanium mesh is as follows: mixing water, nitric acid (more than or equal to 99.0%) and hydrofluoric acid (more than or equal to 38 wt%) according to a volume ratio of 50:10:2 to obtain chemical polishing solution, soaking a titanium mesh for 30s, and sequentially carrying out ultrasonic treatment on deionized water and ethanol for 3-5min.
Rutile TiO 2 Placing the nanorods in a mixed solution of hydrochloric acid, a titanium trichloride solution and deionized water, performing hydrothermal reaction, and performing heat treatment in an air atmosphere to obtain 3D TiO with a nano tree three-dimensional structure and multiple crystal face knots 2 An electrode.
Further, 3D TiO 2 In the preparation process, the volume ratio of the hydrochloric acid to the titanium trichloride solution to the deionized water is 1 (0.2-2.4): 120, the mass fraction of the hydrochloric acid is 36-38%, the concentration of the titanium trichloride solution is 15-20 wt%, the hydrothermal reaction temperature is 80 ℃, the time is 2-5 h, the heat treatment temperature is 400-550 ℃ and the time is 1-3 h.
Further, the 3D BQD@TiO 2 The preparation process of the photoelectrode comprises the following steps:
respectively preparing bismuth nitrate glycol solution and ammonium metavanadate aqueous solution, uniformly mixing, adding hydrochloric acid to obtain mixed solution, and then taking 3D TiO 2 Placing the electrode in a mixed solution, performing hydrothermal reaction, cleaning and drying to obtain the bismuth vanadate quantum dot modified titanium dioxide composite photoelectrode, namely the 3D BQD@TiO 2 And a photoelectrode.
Further, 3D BQD@TiO 2 In the photoelectrode preparation process, the concentration of the bismuth nitrate glycol solution is 0.1-1.0 mM, preferably 0.5mM, the concentration of the ammonium metavanadate aqueous solution is 0.1-1.0 mM, preferably 0.5mM, and the bismuth nitrate glycol solution and the ammonium metavanadate are water-solubleThe volume ratio of the liquid is (1-1.5): 1.
Further, the amount of hydrochloric acid is 25 to 150. Mu.L, preferably 25. Mu.L, and the mass fraction of hydrochloric acid is 36 to 38%.
Furthermore, the temperature of the hydrothermal reaction is 140-200 ℃, preferably 160 ℃, and the time is 4-6 hours, preferably 5 hours.
Furthermore, in the photoelectrocatalysis process, an AM 1.5G filter can be used for simulating solar spectrum, and the light intensity of a light source is 50-200 mW/cm 2 The bias voltage is applied to be +0.2 to +1.0V, the degradation time is 0.5 to 2 hours, and the concentration of the sodium sulfate solution is 0.1mol/L.
Further, in the photoelectrocatalysis process, 3D BQD@TiO may be used 2 And 3D TiO 2 Respectively serving as an anode or a cathode, thereby constructing different photoelectrocatalysis systems. Preferably 3D BQD@TiO 2 As photo anode, 3D TiO 2 As a cathode.
Furthermore, in the photoelectrocatalysis process, the target pollutant can be single bisphenol A, single hexavalent chromium or coexisting bisphenol A and hexavalent chromium, the concentration of the three pollutants is 2-10 mg/L, and the concentration ratio of bisphenol A and hexavalent chromium in the coexisting system is (0.5-5): 1 (the mass concentration of hexavalent chromium here is K) 2 Cr 2 O 7 Meter, the same applies below). Preferably, the target contaminant is bisphenol A and hexavalent chromium co-existing.
In the invention, the titanium mesh substrate is used as a titanium source to provide sites for in-situ growth of titanium dioxide, the uniform vertical nanorods grown by gas phase hydrothermal method are favorable for rapid transfer of electrons, the secondary hydrothermal nanocones and the nanorods form a three-dimensional structure, and the charge transfer and reaction mass transfer efficiency is improved. BiVO with further hydrothermal loading 4 The quantum dot widens the light absorption range of the photoelectrode material due to the narrower band gap width, effectively improves the light absorption efficiency, and forms BiVO 4 /TiO 2 The heterojunction helps to promote rapid separation of the photogenerated charges so that the photogenerated electrons are driven from the BiVO 4 Transfer to TiO 2 And finally transferred to the counter electrode through the titanium mesh substrate. Such 3D BQD@TiO 2 The photoelectrode has high-efficiency stable photoelectrocatalysis performance under simulated sunlight, and can treat bisphenol A and hexa in 30minThe removal rate of the valuable chromium reaches 100 percent.
Compared with the prior art, the invention has the following advantages:
(1) In 3D TiO 2 The substrate electrode has a three-dimensional structure and multiple crystal face crystals, which is helpful for rapid and efficient selective spatial separation of photogenerated carriers on one hand, and provides rich load sites on the other hand with high specific surface area.
(2) In 3D TiO 2 Surface-supported BiVO 4 Quantum dot, biVO 4 The self narrow band gap and quantum confinement effect of the quantum dots help to improve TiO 2 The light absorbing capacity of the photoelectrode widens the light absorbing range to the visible region, and the quantum dot size provides more active sites. Meanwhile, biVO 4 Quantum dot size does not shade TiO 2 Active crystal planes. And BiVO 4 With TiO 2 The energy bands are matched to form heterojunction to promote the hole direction BiVO 4 Transfer of photogenerated electrons to TiO 2 On BiVO 2 /TiO 2 Heterojunction and TiO 2 The interplanar junction synergism further promotes the separation and transfer of photogenerated carriers.
(3) The 3D BQD@TiO prepared by the method 2 The photoelectrode has excellent stability and cyclicity in removing bisphenol A and hexavalent chromium coexisting pollutants in a water body. The photo-generated electron holes of the common photo-catalytic system are all on the photo-catalyst, and the 3D BQD@TiO is prepared by externally applying bias voltage 2 The photo-generated electrons of the photo-anode are further transferred to the cathode through the titanium mesh substrate, so that the separation efficiency and the utilization efficiency of photo-generated charges are effectively improved, and the removal rate of BPA and Cr (VI) still reaches 99.1% and 95.6% respectively after 5 times of circulation. In addition, the externally-applied bias voltage is small, the electric energy consumption is low, and the practical application is facilitated.
(4) The photoelectrocatalysis synergistic system constructed by the invention can realize the efficient photoelectrocatalysis synergistic removal of two pollutants of bisphenol A and hexavalent chromium in water body through mutual synergy of anodic oxidation of bisphenol A and cathodic reduction of hexavalent chromium. And the method can be expanded to remove other combined pollution in the actual water body, such as antibiotics, heavy metal ions, resistance genes and resistance bacteria.
Drawings
FIG. 1 is a 3D BQD@TiO prepared in example 1 2 Scanning electron microscope images of (2);
FIG. 2 is a 3D BQD@TiO prepared in example 1 2 And 3D TiO 2 Is a comparison graph of the photoelectric performance of (a);
FIG. 3 is a 3D BQD@TiO prepared in example 1 2 And 3D TiO 2 A fluorescence spectrum of the photoelectrode and a time-resolved transient fluorescence spectrum;
FIG. 4 is a 3D BQD@TiO prepared in example 1 2 And 3D TiO 2 The removal efficiency of bisphenol A and hexavalent chromium by different cathode-anode combinations and corresponding dynamics fitting curves;
FIG. 5 is a 3D BVO@TiO prepared in comparative example 1 2 And 3D BQD@TiO prepared in example 1 2 Fitting a curve to the single BPA removal efficiency and the corresponding first order kinetics;
FIG. 6 is a graph of quantum size effects in nanocrystals;
FIG. 7 is a 3D BQD@TiO prepared in example 1 2 As photo-anode, platinum sheet and 3D TiO prepared in example 1 2 The removal efficiency of BPA and Cr (VI) in a synchronous removal system used as a cathode and a corresponding dynamics fitting curve;
FIG. 8 is a 3D BQD@TiO prepared in example 1 2 And 3D TiO 2 Respectively serving as an anode and a cathode, and performing removal efficiency on bisphenol A and hexavalent chromium under the conditions of single pollutant and coexisting pollutant and corresponding dynamics fitting curves;
FIG. 9 is a 3D BQD@TiO prepared in example 1 2 And 3D TiO 2 Respectively serving as an anode and a cathode, and removing efficiency and corresponding dynamics fitting curves when bisphenol A and hexavalent chromium with different proportions coexist.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise indicated, the starting materials or processing techniques are all typical commercial products or conventional processing techniques in the art.
Example 1
A method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode specifically comprises the following steps:
(1) Chemical polishing pretreatment: folding metal Ti net into double layers, cutting into 2.5cm×4.5cm size, and adding chemical polishing solution (volume ratio: HNO) 3 :HF:H 2 O=5:1:25), then respectively ultrasonic cleaning in water and ethanol for 3-5min, and soaking in ethanol for standby.
(2) Gas phase hydrothermal: 5mL of deionized water, 300 mu L of hydrogen peroxide (30%) and 1.0mL of hydrochloric acid (37.0 wt%) are added into a reaction kettle liner of a polytetrafluoroethylene substrate, a pretreated dry titanium net is placed on an annular support in the liner, the liner is placed into a high-pressure reaction kettle for gas-phase hydrothermal reaction for 5 hours at 200 ℃, after the reaction is completed, the surface is washed by deionized water, and the surface is naturally dried.
(3) Secondary hydrothermal: adding 25mL of deionized water, 210 mu L of hydrochloric acid (37.0%) and 125 mu L of titanium trichloride solution (18 wt%) into a liner of a reaction kettle, carrying out ultrasonic treatment for 5min to uniformly mix, putting the electrode prepared in the step (2) into the liner, putting the liner into a high-pressure reaction kettle, carrying out hydrothermal reaction at 80 ℃ for 4h, cooling to room temperature after the reaction is finished, flushing the surface with deionized water, and naturally airing.
(4) Calcining in air atmosphere at 450 deg.c and temperature raising rate of 3 deg.c/min for 2 hr to obtain 3D TiO 2 And a photoelectrode.
(5) 15mL of 0.5mM bismuth nitrate glycol solution and an equivalent amount of 0.5mM ammonium metavanadate aqueous solution were added to a reaction kettle liner of 100mL of polytetrafluoroethylene substrate, 25. Mu.L of hydrochloric acid was added thereto, and after mixing uniformly, 3D TiO prepared in example 1 was prepared 2 Placing the photoelectrode into the reactor, performing hydrothermal reaction for 5 hours at 160 ℃, cooling to room temperature after the reaction is completed, flushing the surface with deionized water, and naturally airing to obtain the target electrode 3D0.5BQD@TiO 2 And a photoelectrode. In addition, bismuth nitrate glycol solution and ammonium metavanadate are mixedThe concentration of the aqueous solution was adjusted to 0.25mM and 1.0mM to obtain 3D 0.25BQD@TiO, respectively 2 And 3D 1.0BQD@TiO 2 And a photoelectrode.
(6) 3D TiO prepared by adopting the method 2 With 3D 0.5BQD@TiO 2 Photoelectrodes (abbreviated as 3DBQD@TiO 2 The following is the same), the specific process is as follows:
photoelectrocatalysis experiments were carried out in a 50mL volume cuboid quartz degradation cell using a three electrode system based on 3d bqd@tio 2 And 3D TiO 2 Constructing different double photoelectrode photoelectrocatalysis systems, wherein a saturated calomel electrode is used as a reference electrode, the distance between a working electrode and a counter electrode is 25cm, and the effective photoelectrode area is 2.5X3 cm 2 . The simulated wastewater is 0.1 mol.L -1 A mixed solution of sodium sulfate, 5mg/L bisphenol A and 5mg/L hexavalent chromium was prepared in a volume of 45mL. The light source is a 300W xenon lamp, and the illumination intensity is 100mW/cm 2 And (3) applying a bias voltage of +0.4V (relative to a saturated calomel electrode), performing a photoelectrocatalysis experiment, wherein the reaction time is 1h, sampling at fixed time, testing the concentration of bisphenol A contained in the sample by using Agilent 1260 high performance liquid chromatography, and testing the concentration of hexavalent chromium contained in the sample by using UV 1800. The specific degradation results are shown in FIG. 4. In fig. 4, (a) and (c) represent the removal curves of bisphenol a and hexavalent chromium, respectively, and (b) and (d) represent the corresponding primary kinetics curves.
The test results in FIG. 4 show that 3D BQD@TiO 2 The photoelectrode successfully realizes the efficient photoelectrocatalytic oxidation reduction of the wastewater containing bisphenol A and hexavalent chromium. After 1h of reaction, the removal rates of bisphenol A and hexavalent chromium reach 100%, which shows that 3D BQD@TiO 2 Photoanode and 3D TiO 2 The synergistic photoelectrocatalysis system constructed by the photocathode realizes the efficient and synchronous removal of bisphenol A and hexavalent chromium pollutants in water.
Performance testing
1. Scanning electron microscope analysis
Characterization of the microscopic morphology of the electrode by field emission scanning electron microscopy (Hitachis-4800), see FIG. 1, FIG. 1 showing the TiO prepared in example 1 2 The appearance is a three-dimensional structure, one-dimensional nano rods grow on the titanium mesh substrate, and the diameter is as followsBetween 150 and 250nm, nano cones are grown on the surface of the nano rod and uniformly distributed on the nano rod to form a three-dimensional high-order configuration and a multiple crystal face structure, and the loaded BiVO 4 The quantum dots make the two-dimensional nanometer cone edge round under the condition of not damaging the three-dimensional configuration, and are uniformly distributed on the TiO 2 A surface.
2. Photoelectrochemical property test
The 3D TiO prepared in example 1 was used 2 With 3D BQD@TiO 2 Photoelectrode carries out photoelectrocatalytic oxidation performance research, and comprises the following specific steps:
the photoelectrocatalysis performance test is carried out in a square quartz reaction tank, the electrolyte solution is 0.1mol/L sodium sulfate solution, a three-electrode system is adopted, and 3D TiO is respectively adopted 2 And 3D 0.5BQD@TiO 2 The method comprises the steps of using a platinum sheet as a working electrode, using a saturated calomel electrode as a reference electrode, using a Chen Hua CHI660C electrochemical workstation to test a linear scanning voltammogram curve, a Mort-Schottky curve, a transient photocurrent response curve and an alternating current impedance spectrum, using a xenon lamp as a light source, and using the distance between the light source and the working electrode as 1cm. The test results are shown in FIG. 2, and the results show that under the illumination condition, 3D BQD@TiO 2 The photoresponse property of the electrode is better than that of 3D TiO 2 The photocurrent density can reach 0.8mA/cm 2 Is 3D TiO 2 Is about 600 omega, compared with 3D TiO 2 Reduced by about 0.5 times, and the calculated carrier concentration is 5.96×10 20 cm -3 Compared with 3D TiO 2 The method improves the efficiency by 518 times.
The working electrode is replaced by 3D 0.25BQD@TiO 2 Or 3D 1.0BQD@TiO 2 And (5) performing photoelectrocatalysis performance test. The test result shows that under the illumination condition, 3D 0.25BQD@TiO 2 The photocurrent density of the electrode can reach 0.75mA/cm 2 Impedance is about 650 Ω, carrier concentration is 5.95X10 19 cm -3 。3D 1.0BQD@TiO 2 The photocurrent density of the electrode can reach 0.60mA/cm 2 Impedance is about 900 omega, carrier concentration is 3.05X10 19 cm -3 。
3. Ultraviolet-visible diffuse reflectance test
The 3D TiO prepared in example 1 was used 2 With 3D 0.5BQD@TiO 2 The photoelectrode was subjected to an ultraviolet-visible diffuse reflection test, see FIG. 3a, showing BiVO 4 The loading of the quantum dots facilitates TiO 2 The light absorption range of which is extended to 500nm, FIG. 3b shows that the load BiVO is found by calculation 4 After quantum dot, the bandgap of photoelectrode became 2.8eV, indicating BiVO 4 With TiO 2 Energy band matching to form heterojunction, and obtaining 3D 0.5BQD@TiO 2 The band gap of the photoelectrode becomes smaller, and the light absorption efficiency is improved.
4. Fluorescence spectrum and time-resolved transient fluorescence spectrum test
The 3D TiO prepared in example 1 was used 2 With 3D 0.5BQD@TiO 2 Photoelectrode fluorescence spectrum and time-resolved transient fluorescence spectrum tests, see FIG. 3a, showing BiVO 4 The load of the quantum dots obviously improves the TiO 2 The separation efficiency of photo-generated charges and the life of excited electrons are prolonged (3D TiO 2 ：17.14ns；3D0.5BQD@TiO 2 :19.59 ns) so that more holes reach the surface to participate in oxidation reaction, and the efficiency of oxidative degradation of pollutants is improved.
3D BQD@TiO for highlighting the load of bismuth vanadate in the form of "Quantum dots 2 Advantageously, biVO in the form of "non-quantum dots" prepared by impregnation 4 Coating composite photoelectrode "(3D BVO@TiO) 2 ) For comparison (see comparative example 1 for specific preparation process), 3D BQD@TiO was used respectively 2 And 3D BVO@TiO 2 The effect of removing the single bisphenol A is shown in FIG. 5, using a platinum sheet as the counter electrode. 3D BVO@TiO 2 The removal rate of BPA in 20min is 74.8%, and the kinetic constant is 0.081min -1 Lower than the 3D BQD@TiO of the invention 2 (90.4% removed in 20min, k=0.14 min) -1 ). Description BiVO 4 Loading 3D TiO with Quantum dot size 2 The method is more beneficial to realizing the efficient removal of pollutants.
Most bismuth vanadate-loaded materials are prepared by coating bismuth vanadate on a substrate material, and utilizing the property of bismuth vanadate as a narrow-band semiconductor to realize visible light absorption, so that the synergy of the two materials is neglectedActing; and bismuth vanadate itself has poor charge transport property and short hole diffusion length<70 nm), resulting in severe charge recombination and slow reaction kinetics. The photoelectrocatalysis reaction is used as heterogeneous catalysis interface reaction, the reaction efficiency depends on the light absorption efficiency, the charge separation efficiency and the surface electron injection efficiency of the electrode, and the three efficiencies are comprehensively considered to improve the overall efficiency of the photoelectrocatalysis reaction. Therefore, the 3D BQD@TiO prepared by the method 2 The electrode material has the following unique advantages: on the one hand, the BiVO of quantum dot size 4 Does not shade TiO 2 Photo-generated electron holes in BiVO 4 And TiO 2 After selective separation, electrons pass through TiO 2 The crystal face junction is further separated and finally reaches the counter electrode, so that charge separation and transfer are effectively promoted; on the other hand, quantum dot size materials have quantum confinement effects and quantum size effects, affecting the energy of the semiconductor (as shown in fig. 6), resulting in quantum dot materials and bulk materials having different conduction band positions. With the increase of the band gap, the conduction band edge is transferred to more reduction potential, and the valence band is transferred to more oxidation potential, thereby being beneficial to BiVO 4 With TiO 2 The energy matching forms heterojunction and promotes electron hole separation. Therefore, the bismuth vanadate quantum dot modified titanium dioxide composite photoelectrode can more favorably exert the function of semiconductor heterojunction (BiVO 4 /TiO 2 ) And the titanium dioxide crystal plane junction ({ 111}/{110}/{101 }) to realize the efficient removal of pollutants.
Comparative example 2 (see comparative example 2 for specific procedures) was constructed to simultaneously degrade bisphenol a and hexavalent chromium using a platinum sheet as a counter electrode, and the results are shown in fig. 7, in the same manner as in example 1. Compared with PEC system with platinum sheet as counter electrode, 3D TiO 2 The PEC system as a counter electrode can improve the oxidation efficiency of BPA from 82.0% to 97.4% in 20min, and the corresponding primary kinetic constant is from 0.083min -1 Increasing the temperature to 0.18min -1 The method comprises the steps of carrying out a first treatment on the surface of the The reduction efficiency of Cr (VI) is obviously improved from 12.5 percent to 99.7 percent, and the corresponding kinetic rate constant is also improved from 8 multiplied by 10 percent -4 M -1 min -1 Raised to 0.82M -1 min -1 . The description is based on3D BQD@TiO 2 And 3D TiO 2 The constructed synergistic redox PEC system can simultaneously realize efficient removal of bisphenol A and hexavalent chromium.
In the degradation process, the two pollutants bisphenol A and hexavalent chromium removed by the method have a synergistic removal effect, and 3D TiO is adopted 2 With 3D BQD@TiO 2 The photoelectrode was used to remove the simulated wastewater containing only 5mg/L bisphenol A or hexavalent chromium, and comparative example 3 (see comparative example 3 for specific implementation) was constructed to separately and singly degrade bisphenol A and hexavalent chromium, as shown in FIG. 8. For BPA oxidation, the single BPA removal rate was 89.7% in 20min, and increased to 97.4% when coexisting Cr (VI) was present in the solution; for Cr (VI) reduction, the single Cr (VI) removal rate was 75.9% in 20min, and when coexisting BPA was present in the solution, the Cr (VI) removal rate increased to 99.7%. The result shows that the BPA oxidation and Cr (VI) reduction play a synergistic effect of mutual promotion, and are respectively used as a hole and electron capturing agent, so that the recombination of photo-generated carriers is avoided, and the utilization rate of electron holes is improved.
Comparative example 1:
the preparation method of the bismuth vanadate film modified titanium dioxide composite photoelectrode specifically comprises the following steps:
100mL of 0.5mM Bi (NO) 3 ) 3 ·5H 2 O (ethylene glycol as solvent) as solution A,100mL of 0.5mM NH 4 VO 3 An aqueous solution (ph=3 adjusted with nitric acid) was used as solution B. 3DTiO prepared in example 1 2 The photoelectrode is immersed in the solution a for 30s and then in the solution B for 30s, and the order of the two solutions a and B is exchanged, and this process is repeated 15 times. After the end, the surface of the electrode is washed by deionized water and calcined for 1h under the atmosphere of 500 ℃ to obtain BiVO 4 Film-coated composite photoelectrode 3D BVO@TiO 2 。
Comparative example 2:
compared to example 1, the vast majority are identical, except in this example: in the step (6), the counter electrode is a platinum sheet.
Comparative example 3:
compared to example 1, the vast majority are identical, except in this example:the simulated wastewater in the step (6) is 0.1 mol.L -1 Sodium sulfate solution, single 5mg/L bisphenol A (or 5mg/L hexavalent chromium) mixed solution.
Examples 2 to 3
Compared to example 1, the vast majority are identical, except in this example: the hydrothermal reaction time in the step (5) is respectively 4h and 6h.
Examples 4 to 5
Compared to example 1, the vast majority are identical, except in this example: the hydrothermal reaction temperature in the step (5) is 140 ℃ and 180 ℃ respectively.
Examples 6 to 7
In comparison with example 1 above, the vast majority are identical, except in this example: the concentrations of bisphenol A and hexavalent chromium were adjusted to 2mg/L and 10mg/L, and a photoelectrocatalysis experiment was performed.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode is characterized by using 3D BQD@TiO 2 The photoelectrode is a photo anode and 3D TiO 2 The method comprises the steps of constructing a three-electrode system by taking a saturated calomel electrode as a reference electrode, taking a water body to be treated containing bisphenol A and/or hexavalent chromium as a treatment object, applying bias under the irradiation of a light source, and removing the bisphenol A and the hexavalent chromium in the water body to be treated in a synergistic manner by photoelectrocatalysis.
2. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode as claimed in claim 1Characterized in that the 3D TiO 2 The preparation process of (2) is as follows:
pretreating a metal titanium mesh, placing the pretreated metal titanium mesh in a mixed solution of hydrochloric acid, hydrogen peroxide and water, and performing gas-phase hydrothermal reaction to obtain rutile TiO 2 The volume ratio of hydrochloric acid, hydrogen peroxide and water is (4.2-5.3): 1:17, 36-38% of hydrochloric acid and 30% of hydrogen peroxide;
rutile TiO 2 Placing the nanorods in a mixed solution of hydrochloric acid, a titanium trichloride solution and deionized water, performing hydrothermal reaction, and performing heat treatment in an air atmosphere to obtain 3D TiO with a nano tree three-dimensional structure and multiple crystal face knots 2 An electrode.
3. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode as claimed in claim 2, characterized by that 3D TiO 2 In the preparation process, the volume ratio of the hydrochloric acid to the titanium trichloride solution to the deionized water is 1 (0.2-2.4): 120, the mass fraction of the hydrochloric acid is 36-38%, and the concentration of the titanium trichloride solution is 15-20wt%;
the temperature of the hydrothermal reaction is 80 ℃ and the time is 2-5 h;
the temperature of the heat treatment is 400-550 ℃ and the time is 1-3 h.
4. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode as claimed in claim 1, wherein the 3D BQD@TiO is characterized in that 2 The preparation process of the photoelectrode comprises the following steps:
respectively preparing bismuth nitrate glycol solution and ammonium metavanadate aqueous solution, uniformly mixing, adding hydrochloric acid to obtain mixed solution, and then taking 3D TiO 2 Placing the electrode in a mixed solution, performing hydrothermal reaction, cleaning and drying to obtain the bismuth vanadate quantum dot modified titanium dioxide composite photoelectrode, namely the 3D BQD@TiO 2 And a photoelectrode.
5. A titanium dioxide-based composite according to claim 4A method for removing bisphenol A and hexavalent chromium in sewage by photoelectrode cooperation is characterized in that the method comprises the following steps of 2 In the photoelectrode preparation process, the concentration of the bismuth nitrate glycol solution is 0.1-1.0 mM, the concentration of the ammonium metavanadate aqueous solution is 0.1-1.0 mM, and the volume ratio of the bismuth nitrate glycol solution to the ammonium metavanadate aqueous solution is (1-1.5): 1;
the using amount of the hydrochloric acid is 25-150 mu L, and the mass fraction of the hydrochloric acid is 36-38%.
6. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on the titanium dioxide composite photoelectrode according to claim 4, wherein the hydrothermal reaction is carried out at a temperature of 140-200 ℃ for 4-6 hours.
7. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on the titanium dioxide composite photoelectrode according to claim 1, wherein in the photoelectrocatalysis process, the water body to be treated also contains sodium sulfate with the concentration of 0.1-0.4 mol/L.
8. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on the titanium dioxide composite photoelectrode according to claim 1, wherein the total concentration of bisphenol A and hexavalent chromium in the water to be treated is 2-10 mg/L, and the concentration ratio of bisphenol A to hexavalent chromium is (0.5-5): 1.
9. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on the titanium dioxide composite photoelectrode according to claim 1, wherein the concentration of the bisphenol A and hexavalent chromium in the water to be treated is 2-10 mg/L when the water to be treated contains single bisphenol A;
when containing single hexavalent chromium, the concentration thereof is 2-10 mg/L.
10. The method for cooperatively removing bisphenol A and hexavalent chromium in sewage based on titanium dioxide composite photoelectrode as claimed in claim 1, wherein in the photoelectrocatalysis process, the light intensity of the light source is 50-200 mW/cm 2 ApplyingThe bias voltage is +0.2 to +1.0V, and the degradation time is 0.5 to 2 hours.
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