CN111003760A - Preparation method of photoelectrocatalysis anode material with TNTs as substrate - Google Patents
Preparation method of photoelectrocatalysis anode material with TNTs as substrate Download PDFInfo
- Publication number
- CN111003760A CN111003760A CN201911372217.4A CN201911372217A CN111003760A CN 111003760 A CN111003760 A CN 111003760A CN 201911372217 A CN201911372217 A CN 201911372217A CN 111003760 A CN111003760 A CN 111003760A
- Authority
- CN
- China
- Prior art keywords
- tnts
- titanium plate
- sno
- photoelectrocatalysis
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 26
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000015 trinitrotoluene Substances 0.000 claims abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 58
- 229910052719 titanium Inorganic materials 0.000 claims description 58
- 239000010936 titanium Substances 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003490 Thiodipropionic acid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 10
- 235000019303 thiodipropionic acid Nutrition 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 4
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 230000002779 inactivation Effects 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 9
- 241000588724 Escherichia coli Species 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/30—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
Abstract
The invention discloses a preparation method of a photoelectrocatalysis anode material taking TNTs as a substrate, belonging to the technical field of anode photoelectrocatalysis and pollutant treatment. The anode material has good photoelectric catalytic performance and comprises a substrate TNTs (trinitrotoluene), wherein SnO is loaded on the surface of the substrate2Sb and Ag nano-ions; wherein SnO2And Sb nano particles are attached to the tube bottom and the inner tube wall of the TNTs, and nano Ag ions are loaded at the tube opening of the TNTs, so that a microscopic three-dimensional stable structure is formed. The invention solves the problem of low electric energy utilization rate in the photoelectrocatalysis process, also solves the problem of easy recombination of photoproduction electrons and holes, realizes the high-efficiency and stable performance of photoelectrocatalysis for degrading pollutants, and has the characteristics of stable structure and high photoelectrocatalysis performance. Photoelectric test shows that the TNTs-SnO prepared by the invention2Compared with a pure TNTs anode, the/Sb/Ag photoelectrocatalysis anode has better photochemical property and electrochemical property and has strong removal capability on pollutants.
Description
Technical Field
The invention relates to a preparation method of a photoelectrocatalysis anode material taking TNTs as a substrate, belonging to the technical field of anode photoelectrocatalysis and pollutant treatment.
Background
In recent years, the problems of energy shortage, environmental pollution and the like have attracted people's attention, and the search and development of low-cost clean energy and effective environmental protection technology have become important topics for human sustainable development. The semiconductor photoelectrocatalysis technology can convert low-density solar energy into high-density chemical energy, including degradation and mineralization of various organic pollutants in water and air, hydrogen production by water decomposition, reduction of carbon dioxide and the like. The technology has the advantages of reaction at room temperature, direct utilization of solar energy, no secondary pollution and the like, and has immeasurable significance for fundamentally solving the problems of environmental pollution and energy shortage. Through years of exploration and accumulation of scientists in various countries, research in the field is greatly advanced, but generally speaking, the solar photoelectric catalysis efficiency is still low, and the utilization rate of electric energy is low. One of the main reasons is that the photo-generated electron-hole is easy to recombine, so that the photo-catalytic activity is poor, and the electric energy is used only for further improving the photo-catalytic performance.
Titanium dioxide, a typical semiconductor material, is a promising semiconductor photoelectric catalytic material because it can make full use of the ultraviolet light in sunlight and has suitable valence and conduction band positions. However, like other semiconductor photoelectric catalytic materials, the recombination of electrons and holes generated by the illumination of the semiconductor photoelectric catalytic material seriously restricts the improvement of the activity, and meanwhile, the semiconductor photoelectric catalytic material also has a serious photo-corrosion phenomenon; to this end, researchers have attempted a series of approaches to address this problem, such as morphology control, cocatalyst loading, doping, and the like.
Now with semi-conducting TiO2In the photoelectrocatalysis technology which is a substrate, the utilization rate of light energy and electric energy is low. When the nano Ag particles are loaded on the titanium dioxide, the forbidden band width of the nano Ag particles can be widened, so that the nano Ag particles still have absorption capacity under visible light, and the solar energy can be realizedThe utilization is maximized. And the Sn/Sb ions can further enable the polar plate to have good electrocatalysis capability on the premise of improving the stability of the polar plate. The electric energy in the photoelectrocatalysis process can be fully utilized instead of being used as a bias voltage to improve the photocatalysis performance; therefore, a SnO loaded by taking TNTs as a substrate is developed2a/Sb/Ag photoelectrocatalysis anode.
Disclosure of Invention
The invention aims to provide SnO loaded by taking titanium dioxide nanotube arrays (TNTs) as a substrate2The preparation method of the photoelectric catalytic anode material of/Sb/Ag is used for improving the utilization rate of solar energy and electric energy, and comprises the following steps:
(1) and etching the tightly arranged TNTs on the surface of the pretreated titanium plate by adopting an anodic oxidation method, calcining in an inert atmosphere, washing and drying to obtain the substrate TNTs.
(2) SnO treatment by sol-gel method2And Sb carries out loading: immersing a titanium plate containing TNTs into the precursor solution, taking out, drying at 100-110 ℃ for 14-16 minutes, then thermally decomposing at 440-460 ℃ for 59-61 min, and repeating the operation for 10-15 times to obtain the TNTs-SnO2a/Sb anode, then calcined to make SnO2Sb forms a stable micro three-dimensional structure in the TNTs;
(3) adopting an electrochemical deposition method, taking a platinum sheet as a cathode, taking the material obtained in the step (2) as an anode, loading nano Ag ions to the opening of the TNTs, washing and drying to finally obtain the TNTs loaded SnO with the substrate2A photoelectrocatalysis anode material of/Sb/Ag.
Preferably, the pretreatment process of the titanium plate in the step (1) of the invention is as follows: soaking the titanium plate in NaOH solution for 1 hour, then putting the titanium plate in oxalic acid and nitric acid solution for respectively corroding for 0.5 hour and 6 hours, heating to 90 ℃, then washing and drying the titanium plate by ultrapure water, then putting the titanium plate in mixed solution of acetone and ethanol for 30 minutes by ultrasonic waves, washing and drying the titanium plate by the ultrapure water.
Preferably, the specific process of anodic oxidation in step (1) of the present invention is: putting the pretreated titanium plate into an ethylene glycol system electrolyte taking ammonium fluoride and water as electrolytes, taking Pt as a cathode and the pretreated titanium plate as an anode, and carrying out anodic oxidation on the pretreated titanium plate for 3 hours at constant voltage of 40-60V; washing with water, ultrasonic treating in ethanol solution for 30 min, and air drying; and (3) repeating constant pressure 40-60V treatment on the dried titanium plate for 5-15 minutes, then putting the titanium plate into an ethanol solution for ultrasonic treatment for 30 minutes, and drying the titanium plate.
Preferably, in the step (1) of the present invention, the concentration of ammonium fluoride in the electrolyte is 0.1 to 0.2mol/L, and the volume of water is 1 to 2% of the volume of ethylene glycol.
Preferably, the calcination temperature in the step (1) of the invention is 400-550 ℃ and the calcination time is 0.5-2 h.
Preferably, the precursor solution in the step (2) is a mixed solution of citric acid, ethylene glycol, tin tetrachloride pentahydrate and antimony trichloride, the concentration of the citric acid in the precursor solution is 1.4-6.2 mol/L, the concentration of the tin tetrachloride pentahydrate in the precursor solution is 0.09-0.45 mol/L, and the concentration of the antimony trichloride is 0.01-0.05 mol/L.
Preferably, the calcination in step (2) of the present invention is performed at 400-550 ℃ for 0.5-2 h.
Preferably, the electrolyte in the step (3) is a mixed solution of silver nitrate, sodium perchlorate, ethylenediamine and thiodipropionic acid; the concentration of the silver nitrate in the electrolyte is 0.005-0.02 mol/L; the concentration of sodium perchlorate is 0.06-0.35 mol/L; the concentration of the ethylenediamine is 0.3-1.2 mol/L; the concentration of thiodipropionic acid is 0.01-0.05 mol/L; in the electrolytic process: the voltage is 4V-8V, and the time is 30-60 seconds.
The invention also aims to provide SnO prepared by the method and loaded on TNTs by taking TNTs as substrates2The photoelectric catalytic anode material of/Sb/Ag comprises substrate TNTs, wherein SnO is loaded on the surface of the substrate2Sb and Ag nano-ions; nano Ag ion loaded at TNTs pipe orifice and nano SnO2the/Sb is loaded on the bottom of the TNTs and the inner wall of the pipe.
The nano Ag can generate electron transfer through an electrodeposition method, so that the nano Ag and TNT form stable connection; in addition, the sol-gel method can overcome the surface tension at the opening of the TNT pipe to ensure that SnO2the/Sb can enter the interior of the TNT, so that a stable three-dimensional junction is formedAnd (5) forming.
The invention takes TNTs as a substrate to load SnO2The photoelectrocatalysis anode of/Sb/Ag can be used for photoelectrocatalysis degradation of pollutants (such as photoelectrocatalysis degradation of EE2), photoelectrocatalysis sterilization (such as inactivation of microorganisms in water); it can also be used for treating sewage and soil.
The principle of the invention is as follows: the anode Ag-TNTs can generate electron-hole pair separation, and photo-generated electrons can circulate along an external electric field under the action of the external electric field, so that the electron-hole pair recombination rate is reduced; will decompose water molecule to generate hydroxyl radical (. OH) and photo-generated electron e-Possibly to convert O into2Reduction to oxygen ion radical (O)2 ·-) And SnO under energized conditions2Sb can also generate a large amount of OH, and the active free radicals play a crucial role in the degradation of pollutants. In addition, a large amount of OH generated in the system is not selective per se, can be removed for pollutants and microorganisms in water, and has a large amount of OH generated, so that the degradation effect on the pollutants and the microorganisms is good.
The invention has the beneficial effects that:
(1) the invention adopts the classic semiconductor type material titanium dioxide and makes TiO supported by Ag2The ability to absorb visible light of solar energy; in addition, the load of Ag, Sn and Sb is beneficial to the rapid separation and transfer of photon-generated carriers, so that the photoelectrocatalysis activity of the catalyst is improved; meanwhile, the stability of the polar plate is improved by loading Sn and Sb, and the problem of poor stability is solved.
(2) The novel visible-light-responsive base photoelectrocatalysis material prepared by the invention solves the problems of incomplete energy utilization and unstable polar plate, greatly improves the photoelectrocatalysis performance and the stability of an electrode, realizes the high-efficiency and stable photoelectrocatalysis pollutant degradation performance, and has the characteristics of stable structure, higher photoelectrocatalysis performance and the like.
(3) The electrocatalytic anode has the advantages of simple preparation process, high repeatability, short required time, low cost and low requirement on instruments and equipment; prepared radical photoelectrocatalysisThe material has better photoelectric property under the irradiation of sunlight, and is more traditional TiO2The electrode has a large lift.
Drawings
FIG. 1 shows TNTs-Ag/SnO in example 1 of the present invention2-electron micrographs of Sb electrodes;
FIG. 2 shows TNTs-Ag/SnO in example 1 of the present invention2-a spectrum of Sb electrodes;
FIG. 3 is a graph of diffuse reflection spectra of three different plates in example 1 of the present invention
FIG. 4 is a graph of current-voltage characteristics of three different electrodes in example 1 of the present invention;
FIG. 5 is a graph of the AC impedance of three different plates in example 1 of the present invention;
FIG. 6 shows TNTs-Ag/SnO in example 1 of the present invention2-Sb electrode pair EE2 degradation map;
FIG. 7 shows TNTs-Ag/SnO in example 1 of the present invention2-inactivation of Sb electrode on E.coli.
Detailed Description
The invention is further described with reference to the accompanying drawings, which are not intended to be limiting in any way, and any variations based on the teachings of the invention are intended to fall within the scope of the invention.
Example 1
A preparation method of a photoelectrocatalysis anode material taking TNTs as a substrate specifically comprises the following steps:
(1) selecting a titanium plate with the thickness of 30 multiplied by 0.3mm, placing the titanium plate in NaOH solution for soaking for 1 hour, then placing the titanium plate in oxalic acid solution and nitric acid solution for respectively corroding for 0.5 hour and 6 hours, heating to 90 ℃, finally washing and drying by using ultrapure water, then placing the titanium plate in mixed solution of acetone and ethanol for 30 minutes, washing by using the ultrapure water and drying for later use.
(2) Putting the pretreated titanium plate into 100ml of ethylene glycol system electrolyte taking ammonium fluoride and water as electrolytes (the concentration of the ammonium fluoride is 0.1mol/L, the volume of the water is 1 percent of the volume of the ethylene glycol), taking Pt as a cathode, taking the treated titanium plate as an anode, and carrying out anodic oxidation on the pretreated titanium plate for 3 hours at a constant voltage of 50V; washing with water, ultrasonic treating in ethanol solution for 30 min, and air drying; repeating the constant-pressure 50V treatment on the titanium plate dried previously for 10 minutes; then putting the mixture into an ethanol solution for ultrasonic treatment for 30 minutes, and airing; and calcining the treated titanium plate at 450 ℃ for 2 hours to complete the manufacture of TNTs anode.
(3) Citric acid, ethylene glycol and SnCl4、SbCl3Preparing the precursor containing SnO2And Sb precursor solution (the citric acid in the precursor solution is 1.4mol/L, the stannic chloride is 0.09mol/L, and the antimony trichloride is 0.01mol/L), immersing the titanium plate containing the TNTs prepared in the step (2) into the prepared precursor solution, drying at 105 ℃ for 15 minutes, and then thermally decomposing at 450 ℃ for 1 hour; the above operation was repeated 15 times to obtain TNTs-SnO2the/Sb anode was finally sintered in a tube furnace at 500 ℃ for 2 hours.
(4) Taking AgNO3、NaClO4Dissolving ethylenediamine and thiodipropionic acid in 50ml water (silver nitrate is 0.01mmol/L, sodium perchlorate is 0.1mmol/L, ethylenediamine is 0.6mmol/L, thiodipropionic acid is 0.02mmol/L), using platinum as anode, and TNTs/SnO2Treating 35S with constant 6V voltage by using an-Sb electrode as a cathode, finally washing with water and drying to form the final TNTs-Ag/SnO2-an Sb electrode.
TNTs-Ag/SnO prepared by the embodiment2The final form of the-Sb electrode is shown in figure 1, the titanium dioxide array tubes are tightly arranged, no other substance is used for shielding the tube openings, the photochemical contact area of the titanium dioxide array tubes is ensured, the nano Ag is tightly distributed at the tube openings and connected with the titanium dioxide, the excellence of the photochemical performance of the titanium dioxide array tubes is ensured, the finally manufactured electrode contains Sn and Sb elements, but Sn and Sb are not seen to exist on the surface in figure 1, and further, the fact that the Sn and Sb enter the interior of the titanium dioxide array tubes through a sol-gel method is proved, and a stable structure is formed.
Photoelectric performance test implementation steps:
(1) the finally prepared TNTs-Ag/SnO2the-Sb electrode and the TNTs-Ag and TNTs electrodes are sequentially arranged in 0.1MNa2SO4Using cycles at a scanning rate of 0.1V/sThe ring voltammetry measures the performance of three different plates in a three electrode cell as shown in fig. 4.
(2) The finally prepared TNTs-Ag/SnO2the-Sb electrode and the TNTs-Ag and TNTs electrodes are sequentially arranged in 0.1MNa2SO4In aqueous solution at 10-3～105Applying an alternating voltage of 8mV over the frequency range of Hz the performance of three different plates was measured using the Electrochemical Impedance Spectroscopy (EIS) method, as shown in figure 5.
(3) The finally prepared TNTs-Ag/SnO2the-Sb electrode, the TNTs-Ag electrode and the TNTs electrode are scanned in sequence in the wavelength range of 200-800 nm to obtain a DRS spectrum, as shown in FIG. 3.
As can be seen from fig. 4, the silver loaded composite had lower capacitance but no redox couple was generated. TNT-Ag/SnO2-Sb has obvious oxidation peaks, which indicates that redox reaction exists; this means that TNT-Ag/SnO2-Sb is electrochemically active and can promote redox reactions in an electric field.
FIG. 5EIS shows that the electron transfer resistance varies with Ag and Ag/SnO2The loading of Sb is reduced, and the doping of Ag or SnO2-Sb can effectively enhance the charge transfer of the interface between an electrode and a solution, thereby improving the degradation efficiency; at the same time, the symmetrical and regular shape of the electrochemical impedance spectrum reveals the stability of the electrode in the reaction, which means that there is no corrosion or flaking
Degradation and inactivation experiments of EE2 and e.coli:
the light source is a 250 watt xenon lamp (XE-Y500 model, xenon lamp light source, Beijing Nippon technology Co., Ltd.), and the external voltage is applied by a direct current power supply (HZ-5000 model, North Japan).
The specific EE2 degradation experimental procedure was as follows: (1) firstly, 100ml of EE2 solution with the concentration of 1.2 mg/ml is prepared in a reaction device; (2) with TNTs-Ag/SnO2-Sb electrode as anode, graphite electrode as cathode, solution pH 7, while adding current and illumination; (3) sampling according to a set time period; (4) the withdrawn solution was passed through a liquid phase for determination of the remaining EE2 content, as shown in fig. 6.
TNTs-Ag in FIG. 6SnO2The removal effect of the simulated solar degradation EE2 of the Sb electrode xenon lamp can remove EE2 solution with the concentration of 1.2mg/L to 50 percent after 1h, and the removal capability is very strong.
The specific procedure of the Escherichia coli inactivation experiment is as follows: (1) firstly, the population density is set to be 10 in a reaction device7100ml of CFU/ml bacterial liquid; (2) with TNTs-Ag/SnO2-Sb electrode as anode, graphite electrode as cathode, solution pH 7, while adding current and illumination; (3) sampling according to a set time period; (4) the solution taken out was diluted and plated, and was stored at room temperature for 12 hours and counted as shown in FIG. 7.
FIG. 7 shows TNTs-Ag/SnO2The effect of inactivating escherichia coli under sunlight simulated by an-Sb electrode xenon lamp can ensure that the bacterium density is 107The CFU/mL solution essentially completed inactivation within half an hour.
Example 2
A preparation method of a photoelectrocatalysis anode material taking TNTs as a substrate specifically comprises the following steps:
(1) selecting a titanium plate with the thickness of 30 multiplied by 0.3mm, placing the titanium plate in NaOH solution for soaking for 1 hour, then placing the titanium plate in oxalic acid solution and nitric acid solution for respectively corroding for 0.5 hour and 6 hours, heating to 90 ℃, finally washing and drying by using ultrapure water, then placing the titanium plate in mixed solution of acetone and ethanol for 30 minutes, washing by using the ultrapure water and drying for later use.
(2) Putting the pretreated titanium plate into 100ml of ethylene glycol system electrolyte taking ammonium fluoride and water as electrolytes (the concentration of the ammonium fluoride is 0.2mol/L, the volume of the water is 2 percent of the volume of the ethylene glycol), taking Pt as a cathode, taking the treated titanium plate as an anode, and carrying out anodic oxidation on the pretreated titanium plate for 3 hours at a constant voltage of 40V; washing with water, ultrasonic treating in ethanol solution for 30 min, and air drying; repeating the constant-pressure 40V treatment on the titanium plate dried previously for 15 minutes; then putting the mixture into an ethanol solution for ultrasonic treatment for 30 minutes, and airing; the treated titanium plate was calcined at 400 ℃ for 1.5 hours and the TNTs anode was completed.
(3) Citric acid, ethylene glycol and SnCl4、SbCl3Is a precursor ofPreparation of raw materials containing SnO2And Sb precursor solution (the citric acid in the precursor solution is 3mol/L, the stannic chloride is 0.3mol/L, and the antimony trichloride is 0.03mol/L), immersing the titanium plate containing the TNTs prepared in the step (2) into the prepared precursor solution, drying for 14 minutes at 100 ℃, and then thermally decomposing for 1 hour at 440 ℃; the above operation was repeated 10 times to obtain TNTs-SnO2the/Sb anode was finally sintered in a tube furnace at 400 ℃ for 2 hours.
(4) Taking AgNO3、NaClO4Dissolving ethylenediamine and thiodipropionic acid in 50ml water (silver nitrate is 0.05mmol/L, sodium perchlorate is 0.06mmol/L, ethylenediamine is 0.3mmol/L, thiodipropionic acid is 0.01mmol/L), using platinum as anode, and TNTs/SnO2Treating the cathode with-Sb electrode at constant 2V for 60S, washing with water, and air drying to obtain TNTs-Ag/SnO2-an Sb electrode.
(5) The same measurement method as in example 1 was applied to the prepared TNTs-Ag/SnO2-the inactivation of escherichia coli and the degradation capacity of pollutants by Sb electrodes are determined; the EE2 can be removed to 47% after 1 hour by using EE2 solution with the concentration of 1.2mg/L, and the removal capability is stronger than that of a plurality of methods; in addition, the inactivation capacity of the strain to Escherichia coli can ensure that the strain density is 107The CFU/mL solution essentially completed inactivation within half an hour.
Example 3
A preparation method of a photoelectrocatalysis anode material taking TNTs as a substrate specifically comprises the following steps:
(1) selecting a titanium plate with the thickness of 30 multiplied by 0.3mm, placing the titanium plate in NaOH solution for soaking for 1 hour, then placing the titanium plate in oxalic acid solution and nitric acid solution for respectively corroding for 0.5 hour and 6 hours, heating to 90 ℃, finally washing and drying by using ultrapure water, then placing the titanium plate in mixed solution of acetone and ethanol for 30 minutes, washing by using the ultrapure water and drying for later use.
(2) Putting the pretreated titanium plate into 100ml of ethylene glycol system electrolyte taking ammonium fluoride and water as electrolytes (the concentration of the ammonium fluoride is 0.15mol/L, the volume of the water is 1.5 percent of the volume of the ethylene glycol), taking Pt as a cathode, taking the treated titanium plate as an anode, and carrying out anodic oxidation on the pretreated titanium plate for 3 hours at a constant voltage of 60V; washing with water, ultrasonic treating in ethanol solution for 30 min, and air drying; repeating the constant-pressure 60V treatment on the titanium plate dried previously for 13 minutes; then putting the mixture into an ethanol solution for ultrasonic treatment for 30 minutes, and airing; the treated titanium plate was calcined at 550 ℃ for 0.5 hour to complete the fabrication of TNTs anodes.
(3) Citric acid, ethylene glycol and SnCl4、SbCl3Preparing the precursor containing SnO2And Sb precursor solution (the citric acid in the precursor solution is 6.2mol/L, the stannic chloride is 0.45mol/L, and the antimony trichloride is 0.05mol/L), immersing the titanium plate containing the TNTs prepared in the step (2) into the prepared precursor solution, drying for 16 minutes at 110 ℃, and then thermally decomposing for 1 hour at 460 ℃; the above operation was repeated 13 times to obtain TNTs-SnO2the/Sb anode was finally sintered in a tube furnace at 550 ℃ for 0.5 hour.
(4) Taking AgNO3、NaClO4Dissolving ethylenediamine and thiodipropionic acid in 50ml water (wherein silver nitrate is 0.03mmol/L, sodium perchlorate is 0.35mmol/L, ethylenediamine is 1.2mmol/L, thiodipropionic acid is 0.05mmol/L), using platinum as anode, and TNTs/SnO2Treating the cathode with-Sb electrode at constant voltage of 10V for 50S, washing with water, and air drying to obtain TNTs-Ag/SnO2-an Sb electrode.
(5) The same measurement method as that in example 1 is used for measuring the inactivation of escherichia coli and the degradation capability of pollutants on the prepared TNTs-Ag/SnO2-Sb electrode; the EE2 can be removed to about 48% after 1 hour by using EE2 solution with the concentration of 1.2mg/L, and the removal capability is stronger than that of a plurality of methods; in addition, the inactivation capacity of the strain to Escherichia coli can enable the solution with the strain density of 107CFU/mL to basically complete inactivation within half an hour.
In the process of loading the nano Ag, the length of the electrifying time and the voltage can influence the quantity and the form of the loaded Ag; the over-high voltage can cause the reaction process to be rapid and violent, the dispersibility of Ag on the surface of the polar plate is poor, a large amount of large crystals appear, and partial pipe orifices are covered, so that the photochemical performance is influenced; the voltage is too low, and although the problem of dispersibility is solved, the load is too low, so that an ideal photoelectric effect cannot be achieved; therefore, the obtained voltage can meet the experimental requirements when the voltage is 4-8V by testing different voltages.
Claims (9)
1. A preparation method of a photoelectrocatalysis anode material taking TNTs as a substrate is characterized by comprising the following steps:
(1) etching closely arranged TNTs on the surface of the pretreated titanium plate by adopting an anodic oxidation method, calcining in an inert atmosphere, washing and drying to obtain a substrate TNTs;
(2) SnO treatment by sol-gel method2And Sb carries out loading: immersing a titanium plate containing TNTs into the precursor solution, taking out, drying at 100-110 ℃ for 14-16 minutes, then thermally decomposing at 440-460 ℃ for 59-61 min, and repeating the operation for 10-15 times to obtain the TNTs-SnO2a/Sb anode, then calcined to make SnO2Sb forms a stable micro three-dimensional structure in the TNTs;
(3) adopting an electrochemical deposition method, taking a platinum sheet as a cathode, taking the material obtained in the step (2) as an anode, loading nano Ag ions to the opening of the TNTs, washing and drying to finally obtain the TNTs loaded SnO with the substrate2A photoelectrocatalysis anode material of/Sb/Ag.
2. The method according to claim 1, wherein the pretreatment process of the titanium plate in the step (1) is as follows: soaking the titanium plate in NaOH solution for 1 hour, then putting the titanium plate in oxalic acid and nitric acid solution for respectively corroding for 0.5 hour and 6 hours, heating to 90 ℃, then washing and drying the titanium plate by ultrapure water, then putting the titanium plate in mixed solution of acetone and ethanol for 30 minutes by ultrasonic waves, washing and drying the titanium plate by the ultrapure water.
3. The method of claim 1, further comprising: the specific process of anodic oxidation in the step (1) is as follows: putting the pretreated titanium plate into an ethylene glycol system electrolyte taking ammonium fluoride and water as electrolytes, taking Pt as a cathode and the pretreated titanium plate as an anode, and carrying out anodic oxidation on the pretreated titanium plate for 3 hours at constant voltage of 40-60V; washing with water, ultrasonic treating in ethanol solution for 30 min, and air drying; and (3) repeating constant pressure 40-60V treatment on the dried titanium plate for 5-15 minutes, then putting the titanium plate into an ethanol solution for ultrasonic treatment for 30 minutes, and drying the titanium plate.
4. The method of claim 3, further comprising: the concentration of ammonium fluoride in the electrolyte is 0.1-0.2 mol/L, and the volume of water is 1-2% of that of the glycol.
5. The method of claim 1 or 4, wherein: in the step (1), the calcining temperature is 400-550 ℃ and the time is 0.5-2 h.
6. The method of claim 1, further comprising: the precursor solution in the step (2) is a mixed solution of citric acid, ethylene glycol, tin tetrachloride pentahydrate and antimony trichloride, the concentration of the citric acid in the precursor solution is 1.4-6.2 mol/L, the concentration of the tin tetrachloride pentahydrate in the precursor solution is 0.09-0.45 mol/L, and the concentration of the antimony trichloride in the precursor solution is 0.01-0.05 mol/L.
7. The method of claim 1, further comprising: the calcining condition in the step (2) is sintering for 0.5 h-2 h at 400 ℃ -550 ℃.
8. The method of claim 2, further comprising: the electrolyte in the step (3) is a mixed solution of silver nitrate, sodium perchlorate, ethylenediamine and thiodipropionic acid; the concentration of the silver nitrate in the electrolyte is 0.005-0.02 mol/L; the concentration of sodium perchlorate is 0.06-0.35 mol/L; the concentration of the ethylenediamine is 0.3-1.2 mol/L; the concentration of thiodipropionic acid is 0.01-0.05 mol/L, the processing voltage is 4V-8V, and the processing time is 30-60 seconds.
9. SnO loaded on TNTs (trinitrotoluene) prepared by using method of any one of claims 1 to 8 as substrate2The photoelectric catalytic anode material of/Sb/Ag comprises substrate TNTs, wherein SnO is loaded on the surface of the substrate2Sb and Ag nano-ions; nano Ag ion loaded at TNTs pipe orifice and nano SnO2the/Sb is loaded on TNTs at the bottom and on the inner wall of the tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911372217.4A CN111003760A (en) | 2019-12-27 | 2019-12-27 | Preparation method of photoelectrocatalysis anode material with TNTs as substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911372217.4A CN111003760A (en) | 2019-12-27 | 2019-12-27 | Preparation method of photoelectrocatalysis anode material with TNTs as substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111003760A true CN111003760A (en) | 2020-04-14 |
Family
ID=70118776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911372217.4A Pending CN111003760A (en) | 2019-12-27 | 2019-12-27 | Preparation method of photoelectrocatalysis anode material with TNTs as substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111003760A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374585A (en) * | 2020-09-18 | 2021-02-19 | 昆明理工大学 | Method for simultaneously removing antibiotics and resistant bacteria in water environment |
| CN114242981A (en) * | 2021-12-17 | 2022-03-25 | 太原理工大学 | TiO 22-SnO2Composite material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949990A (en) * | 2011-08-16 | 2013-03-06 | 同济大学 | Macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method |
| CN103055855A (en) * | 2013-01-12 | 2013-04-24 | 桂林理工大学 | Preparation method of Ag/TiO2 nanotube array and application of photocatalytically degrading sugar preparing wastewater |
| KR20130083332A (en) * | 2012-01-12 | 2013-07-22 | 경북대학교 산학협력단 | Bifacial anode for water treatment with photoelectrocatalytic layer and electrocatalytic layer, a preparation method thereof and a water treatment method using the same |
| CN104176795A (en) * | 2014-08-28 | 2014-12-03 | 扬州大学 | Preparation method for titanium dioxide nanotube loaded with macroporous antimony tin oxide |
| CN104593818A (en) * | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN105603492A (en) * | 2016-01-29 | 2016-05-25 | 武汉理工大学 | Method for electrochemically depositing silver nanoparticles in titanium dioxide nanotube array |
| CN105712428A (en) * | 2016-02-01 | 2016-06-29 | 南京理工大学 | Antimony-doped tin oxide-carbon nanotube compounded adsorptive electrode and preparation method thereof |
| US9502182B2 (en) * | 2013-01-23 | 2016-11-22 | Research & Business Foundation Sungkyunkwan University | Solar cell and method of manufacturing the same |
| CN107804900A (en) * | 2017-10-27 | 2018-03-16 | 东华理工大学 | A kind of steady photovoltaic electrodes of titanium-based type and its preparation method and application |
-
2019
- 2019-12-27 CN CN201911372217.4A patent/CN111003760A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949990A (en) * | 2011-08-16 | 2013-03-06 | 同济大学 | Macroporous tin dioxide-titanium dioxide nanotube composite electrode and its preparation method |
| KR20130083332A (en) * | 2012-01-12 | 2013-07-22 | 경북대학교 산학협력단 | Bifacial anode for water treatment with photoelectrocatalytic layer and electrocatalytic layer, a preparation method thereof and a water treatment method using the same |
| CN103055855A (en) * | 2013-01-12 | 2013-04-24 | 桂林理工大学 | Preparation method of Ag/TiO2 nanotube array and application of photocatalytically degrading sugar preparing wastewater |
| US9502182B2 (en) * | 2013-01-23 | 2016-11-22 | Research & Business Foundation Sungkyunkwan University | Solar cell and method of manufacturing the same |
| CN104176795A (en) * | 2014-08-28 | 2014-12-03 | 扬州大学 | Preparation method for titanium dioxide nanotube loaded with macroporous antimony tin oxide |
| CN104593818A (en) * | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN105603492A (en) * | 2016-01-29 | 2016-05-25 | 武汉理工大学 | Method for electrochemically depositing silver nanoparticles in titanium dioxide nanotube array |
| CN105712428A (en) * | 2016-02-01 | 2016-06-29 | 南京理工大学 | Antimony-doped tin oxide-carbon nanotube compounded adsorptive electrode and preparation method thereof |
| CN107804900A (en) * | 2017-10-27 | 2018-03-16 | 东华理工大学 | A kind of steady photovoltaic electrodes of titanium-based type and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| PEIQIANG LI等: "Constructing Stake Structured TiO2-NTs/Sb-Doped SnO2 Electrode Simultaneously with High Electrocatalytic and Photocatalytic Performance for Complete Mineralization of Refractory Aromatic Acid", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| XU ANLIN等: "Preparation and characterization of a TiO2-NT/SnO2-Sb tubular porous electrode with long service lifetime for wastewater treatment process", 《RSC ADVANCES》 * |
| XU LIU等: "Electrodeposition preparation of Ag nanoparticles loaded TiO2 nanotube arrays with enhanced photocatalytic performance", 《APPLIED SURFACE SCIENC》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374585A (en) * | 2020-09-18 | 2021-02-19 | 昆明理工大学 | Method for simultaneously removing antibiotics and resistant bacteria in water environment |
| CN112374585B (en) * | 2020-09-18 | 2023-03-21 | 昆明理工大学 | Method for simultaneously removing antibiotics and resistant bacteria in water environment |
| CN114242981A (en) * | 2021-12-17 | 2022-03-25 | 太原理工大学 | TiO 22-SnO2Composite material and preparation method and application thereof |
| CN114242981B (en) * | 2021-12-17 | 2024-04-09 | 太原理工大学 | TiO (titanium dioxide) 2 -SnO 2 Composite material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zou et al. | NixSy nanowalls/nitrogen‐doped graphene foam is an efficient trifunctional catalyst for unassisted artificial photosynthesis | |
| Kim et al. | Improving stability and photoelectrochemical performance of BiVO4 photoanodes in basic media by adding a ZnFe2O4 layer | |
| Liu et al. | Efficient electricity production and simultaneously wastewater treatment via a high-performance photocatalytic fuel cell | |
| Dong et al. | Remarkable enhancement on photoelectrochemical water splitting derived from well-crystallized Bi2WO6 and Co (OH) x with tunable oxidation state | |
| CN105749914B (en) | A kind of method of symmetrical difunctional photochemical catalyst, dual chamber Photoreactor and photocatalytic reduction of carbon oxide | |
| CN110655656A (en) | Cobalt metal organic framework material and preparation method and application thereof | |
| Sun et al. | Effect of light irradiation on the photoelectricity performance of microbial fuel cell with a copper oxide nanowire photocathode | |
| CN108906080B (en) | CdS/Cu2S/Co-based photoelectric catalytic material and preparation method thereof | |
| CN111068639A (en) | Zinc oxide doped mixed crystal type titanium dioxide nanotube photocatalytic composite material | |
| CN110205638B (en) | Z-shaped CuBi2O4/SnO2Photoelectric cathode film and preparation method and application thereof | |
| CN102534725A (en) | Method for preparing Ag2S-doped TiO2 nanotube electrode | |
| CN111003760A (en) | Preparation method of photoelectrocatalysis anode material with TNTs as substrate | |
| Wang et al. | Dual-doping in the bulk and the surface to ameliorate the hematite anode for photoelectrochemical water oxidation | |
| CN102534718B (en) | Method for preparing PbO2-modified TiO2 nanotube electrode | |
| CN107841763B (en) | A kind of optoelectronic pole and preparation method thereof based on the regulation of surface hydrogen-oxygen shell | |
| CN116641066B (en) | Photoelectrocatalysis material and preparation method thereof | |
| Leng et al. | Enhanced quinoline degradation by 3D stack Z-scheme photoelectrocatalytic system with Ag-TNTs photoanode and CN-CNWs photocathode | |
| CN105826081A (en) | Titanium-dioxide-based nanorod array counter electrode and preparation method and application thereof | |
| WO2024051019A1 (en) | Preparation method for quantum dot sensitized composite photo-anode, and quantum dot sensitized composite photo-anode and use therof | |
| CN111778518B (en) | High-performance P: Fe 2 O 3 /FeOOH composite photoelectrode and preparation method and application thereof | |
| CN106745534B (en) | Composite photocatalytic electrode of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p-n heterojunction and preparation method thereof | |
| CN114804303A (en) | System and method for degrading organic pollutants in water body and recovering heavy metal ions at same time | |
| CN104230179B (en) | A kind of ultra-thin, preparation method of extra granular nanometer a phase ferricoxide thin film | |
| Morgante et al. | Microbial bioelectrochemical cells for hydrogen generation based on irradiated semiconductor photoelectrodes | |
| Zhang et al. | Anode modified by BiFeO3 and application in resourceful treatment of salty organic wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200414 |
|
| RJ01 | Rejection of invention patent application after publication |