CN111807475A - Titanium-based diamond-doped lead dioxide electrode and catalytic degradation technology thereof for bentazon - Google Patents
Titanium-based diamond-doped lead dioxide electrode and catalytic degradation technology thereof for bentazon Download PDFInfo
- Publication number
- CN111807475A CN111807475A CN201910284654.4A CN201910284654A CN111807475A CN 111807475 A CN111807475 A CN 111807475A CN 201910284654 A CN201910284654 A CN 201910284654A CN 111807475 A CN111807475 A CN 111807475A
- Authority
- CN
- China
- Prior art keywords
- electrode
- electrodeposition
- diamond
- titanium
- preparing
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000010936 titanium Substances 0.000 title claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 12
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title abstract description 24
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 title abstract description 17
- 230000003197 catalytic effect Effects 0.000 title abstract description 9
- 230000015556 catabolic process Effects 0.000 title description 3
- 238000006731 degradation reaction Methods 0.000 title description 3
- 238000004070 electrodeposition Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000002113 nanodiamond Substances 0.000 claims abstract description 11
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 6
- 239000010432 diamond Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 229910052787 antimony Inorganic materials 0.000 claims 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910000464 lead oxide Inorganic materials 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 150000001462 antimony Chemical class 0.000 abstract description 2
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- -1 hydroxyl free radical Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000005476 Bentazone Substances 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- CNBGNNVCVSKAQZ-UHFFFAOYSA-N benzidamine Natural products C12=CC=CC=C2C(OCCCN(C)C)=NN1CC1=CC=CC=C1 CNBGNNVCVSKAQZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a titanium-based diamond-doped lead dioxide electrode and a technology for catalyzing and degrading bentazon by using the same. The preparation method comprises the steps of taking a titanium plate as a substrate, dissolving tin salt and antimony salt according to a certain proportion to form coating liquid, forming tin-antimony oxide through coating and thermal decomposition to serve as a middle layer, preparing diamond-modified beta-PbO 2 on the lead oxide middle layer by adopting an electrodeposition technology, and using doped nano-diamond particles as catalytic active sites to improve the electrocatalysis of an electrode. The lead oxide electrode modified by diamond obtained by the invention is compact and uniform, has small particle size and larger catalytic active area. Meanwhile, the surface active layer has strong adhesive force and is not easy to fall off; the surface is smooth and firm, can resist acid and alkali corrosion, and has good catalytic activity and service life. In addition, the method has the advantages of simple process conditions, low cost and stable performance of the obtained product, is suitable for industrial production, can be widely applied to the field of sewage treatment by an electrocatalytic oxidation technology, and has a far-reaching market prospect.
Description
Technical Field
The invention relates to a nano-diamond doped lead dioxide composite electrode for removing bentazone in water by oxidation and a preparation method thereof, in particular to a metal oxide with catalytic activity prepared on a titanium plate by heat deposition and electrodeposition, wherein doped nano-diamond particles can be used as catalytic activity sites so as to promote the electrocatalysis of the electrode, and the bentazone in water is oxidized into inorganic matters by electrocatalysis reaction, belonging to the application field of water treatment technology.
Background
The problem of sewage treatment has been the focus of research. With the development of agricultural technology, more and more pesticides are used for crop production, and most of these pollutants are organic pollutants which, when discharged into water, can cause damage to the ecological environment. In the sewage treatment technology, the electrocatalytic oxidation method has low requirements on equipment, high treatment speed, simple and convenient operation, cleanness, no pollution and easy large-scale application, and is an environment-friendly technology. Has been paid extensive attention in recent years, and is an important development direction in the field of sewage treatment in the future. The nature of the anode electrode material has a critical influence on the efficiency of the electrocatalytic oxidation process.
At present, electrocatalytic oxidation is one of advanced oxidation methods, and has the advantages of no need of adding chemicals, small equipment, suitability for combined use with other methods and the like. The anode of electrocatalytic oxidation can generate hydroxyl free radical (. OH) with strong oxidizability in the sewage treatment process, so that organic matters are converted into small molecular organic acid after ring opening or chain breaking, and even completely oxidized into CO2 and H2O. The process for effectively treating the wastewater as a hardly biodegradable organic matter is very worthy of popularization and popularity. A boron-doped diamond (BDD) film is used as an electrode material in a plurality of electrodes, and the special sp3 bond structure and the electrical conductivity of the BDD film endow the BDD electrode with excellent electrochemical characteristics, such as a wide electrochemical potential window, low background current, good physical and chemical stability, low adsorption characteristic and the like. In addition, the diamond is a physical adsorption to hydroxyl radicals and does not react with the surface of the electrode chemically, so that the radicals generated in the polarization process can catalyze, oxidize and degrade organic matters more efficiently, and oxygen evolution side reactions are less. However, the BDD electrode is expensive in manufacturing cost, and if the BDD electrode is put into wastewater treatment in a large scale, great economic investment is caused, and the profitability of enterprises is influenced. The PbO2 electrode has the advantages of high oxygen evolution potential, good stability, good conductivity, corrosion resistance, low price and the like, and has been used as an anode in industrial production for a long time. However, compared with the BDD electrode, the amount of hydroxyl radicals generated is smaller, and thus PbO2 is less catalytically active than the BDD electrode. In addition, the PbO2 coating has large internal stress, and nascent oxygen generated in the electrolytic process is easy to diffuse to the substrate through the surface layer, so that the substrate is passivated, the coating falls off, and the electrochemical stability and the service life of the electrode are reduced. It was found that the internal stress of the PbO2 electrode can be effectively relieved by adding a small amount of nanoparticles (for example, ZrO2, CeO2 and the like) into the plating solution, but the doping of the nanoparticles can not effectively improve the catalytic activity of the PbO2 electrode at the same time. This patent proposes, utilizes nanometer diamond powder modified lead oxide electrode, can increase the active site on electrode surface on the one hand, and the internal stress of lead oxide cladding material can be alleviated in the doping of nanometer particle on the one hand to improve the stability of electrode, finally prepare out the lead oxide electrode similar with BDD electrode catalytic activity.
Disclosure of Invention
According to the defects of the prior art, the invention provides a preparation method of a nanoparticle modified electrode with low manufacturing cost, high activity and stable chemical properties.
The technical scheme of the invention is as follows: dissolving antimony salt, tin salt, an alcohol solution and an acid solution according to a certain proportion to form a coating solution by taking a titanium plate as a substrate, forming tin-antimony oxide as an intermediate layer by coating and thermal decomposition, and preparing diamond-modified beta-PbO 2 on the intermediate layer by adopting an electrodeposition technology.
Wherein, the preferred scheme is as follows:
the intermediate layer coating liquid comprises the following components: 3-25 mL of isopropanol, 0.1-8 mL of concentrated hydrochloric acid, 0.5-10 g of stannic chloride pentahydrate, and 0.1-8 g of antimony trichloride.
The number of times of coating the intermediate layer is different from 5 times to 10 times.
The high-temperature calcination can be carried out at a temperature of 250 ℃ to 800 ℃ and a time of 10min to 60 min.
The current density of the electrodeposition is 20mA/cm 2-50 mA/cm2, the total electrodeposition time is 0.5-1h, the electrodeposition temperature is 25-100 ℃, the electrode spacing is 2.5cm, and the electrodeposition solution comprises 0.1-1 mol/L Pb (NO3)2, 0.05-2 mol/L HNO3, 0.5-2 g/L NaF and 10-200 mg/L nano-diamond.
The invention has the advantages that:
(1) and the doping of the nano-diamond can increase the active sites on the surface of the electrode by doping with common metal nano-particles, so that the degradation rate of pollutants is accelerated.
(2) The internal stress of the lead oxide coating can be reduced through the doping of the nano particles, so that the stability of the electrode is improved.
(3) The extremely stable chemical property of the diamond nano-particles enables the PbO2 electrode to maintain certain electrocatalytic activity in the long-term use process.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
and (3) polishing the titanium sheet by using sand paper, carrying out alkali washing to remove oil, carrying out oxalic acid etching, ultrasonically cleaning by using deionized water, and then naturally airing.
3.506g of stannic chloride and 0.261g of antimony trichloride are weighed and dissolved in 20mL of isopropanol, then 1mL of hydrochloric acid is weighed and uniformly mixed with the solution, magnetic stirring is adopted until the solution is uniform and stable, the coating solution is dipped by a writing brush and coated on a titanium mesh, then the titanium mesh is placed in an electrothermal constant-temperature drying oven to be dried for 15min at the temperature of 100 ℃, and then the titanium mesh is roasted for 10min at the temperature of 450 ℃ in a muffle furnace. And then taken out for brushing again. After repeating this for 9 times, the resultant was baked in a muffle furnace at 500 ℃ for 1 hour to obtain an intermediate layer.
The surface active layer of the beta-PbO 2 is obtained by electrodeposition, the electrodeposition solution is 0.5mol/L Pb (NO3)2, 0.1mol/L HNO3 and 0.04mol/L NaF, and the current density is 30mA/cm 2. And carrying out electrodeposition for 0.5h at the temperature of 65 ℃ to obtain the undoped lead dioxide electrode.
The electrode is used as the bentazon in the anodic oxidation water, the initial concentration of the bentazon is 100mg/L, the working area is 24cm2 under the conditions of room temperature and acidic pH value, the reaction is carried out for 240min, and the removal rate of the bentazon reaches about 48%.
Example 2:
the pretreatment of the titanium sheet and the preparation of the intermediate layer were as in example 1, except for the components of the bath. The surface active layer of the beta-PbO 2 is obtained by electrodeposition, the used electrodeposition solution is 0.5mol/L Pb (NO3)2, 0.1mol/L HNO3, 0.04mol/L NaF and 0.5g/L nano-diamond powder, and the used current density is 30mA/cm 2. The temperature is 65 ℃, and the electrodeposition is carried out for 0.5h, thus obtaining the lead dioxide electrode with the doping amount of 0.5 g/L.
The electrode is used as bentazon in anodic oxidation water, the initial concentration of the bentazon is 100mg/L, the working area is 24cm2 under the conditions of room temperature and acidic pH value, the reaction is carried out for 240min, the removal rate of the bentazon reaches about 90%, and the service life of the electrode is prolonged.
Example 3:
titanium sheet pretreatment and intermediate layer preparation methods were as in example 1, except that the components of the electrodeposition bath were electrodeposited to obtain a β -PbO2 surface active layer using 0.5mol/L Pb (NO3)2, 0.1mol/L HNO3, 0.04mol/L NaF, 1g/L nanodiamond powder, and using a current density of 30mA/cm 2. The temperature is 65 ℃, and the electrodeposition is carried out for 0.5h, thus obtaining the lead dioxide electrode with the doping amount of 1 g/L.
The electrode is used as bentazon in anodic oxidation water, the initial concentration of the bentazon is 100mg/L, the working area is 24cm2 under the conditions of room temperature and acidic pH value, the reaction is carried out for 240min, the removal rate of the bentazon reaches about 94%, and the service life of the electrode is prolonged.
Example 4:
titanium sheet pretreatment and intermediate layer preparation methods were as in example 1, except that the components of the electrodeposition bath were electrodeposited to obtain a β -PbO2 surface active layer using 0.5mol/L Pb (NO3)2, 0.1mol/L HNO3, 0.04mol/L NaF, 2g/L nanodiamond powder, and using a current density of 30mA/cm 2. The temperature is 65 ℃, and the electrodeposition is carried out for 0.5h, thus obtaining the lead dioxide electrode with the doping amount of 2 g/L.
The electrode is used as bentazon in anodic oxidation water, the initial concentration of the bentazon is 100mg/L, the working area is 24cm2 under the conditions of room temperature and acidic pH value, the reaction is carried out for 240min, the removal rate of the bentazon reaches about 90%, and the service life of the electrode is prolonged.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (8)
1. The technology is characterized in that soluble antimony and tin salt are dissolved in an alcohol solvent to prepare a middle layer precursor coating solution, an Sb-SnO2 middle layer is prepared by a coating-drying-thermal sintering method, a beta-PbO 2 catalyst layer is electroplated by an electrodeposition method, a certain amount of nano-diamond powder is added into the electrodeposition solution, and finally the diamond nano-doped modified lead oxide electrode is obtained.
2. A method for preparing the electrode of claim 1, wherein the anode used for electrodeposition is a titanium sheet, a titanium mesh, graphite, stainless steel, a platinum sheet, or the like.
3. The method for preparing the electrode according to claim 1, wherein a brush pen is used for dipping antimony and tin coating liquid, the pretreated titanium plate is coated for 5-10 times, the drying temperature is 80-100 ℃, the calcining temperature is 400-600 ℃, and the time can be varied from 10-60 min.
4. A method for preparing the electrode according to claim 1, wherein the electrolyte solution is an organic substance selected from the group consisting of nitrate, sulfate, sulfamate, tetrahydrofuran, and benzene.
5. The method for preparing the electrode according to claim 1, wherein the concentration of the nanodiamond in the electrodeposition solution is 0.5 to 2 mol/L.
6. The size of the nano diamond is different from 20-50 nm.
7. A method for preparing the electrode according to claim 1, wherein the concentration of boric acid is varied from 0.1 to 0.5 mol/L.
8. An electrodeposition condition as set forth in claim one wherein: the deposition temperature is 60-70 ℃, the current density is 20-40 mA/cm2, the deposition time is 0.5-1h, the stirring speed is about 300-500 r/min in the electrodeposition process, the distance between the polar plates is 1.5-5cm, and the pH value is 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910284654.4A CN111807475A (en) | 2019-04-10 | 2019-04-10 | Titanium-based diamond-doped lead dioxide electrode and catalytic degradation technology thereof for bentazon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910284654.4A CN111807475A (en) | 2019-04-10 | 2019-04-10 | Titanium-based diamond-doped lead dioxide electrode and catalytic degradation technology thereof for bentazon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111807475A true CN111807475A (en) | 2020-10-23 |
Family
ID=72844464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910284654.4A Pending CN111807475A (en) | 2019-04-10 | 2019-04-10 | Titanium-based diamond-doped lead dioxide electrode and catalytic degradation technology thereof for bentazon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111807475A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477371A (en) * | 2022-09-05 | 2022-12-16 | 湖南新锋科技有限公司 | Diamond-lead oxide doped coupling electrode and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108301013A (en) * | 2018-02-14 | 2018-07-20 | 中氧科技（广州）有限公司 | A kind of preparation method for the modified anode of lead dioxide generating ozone |
-
2019
- 2019-04-10 CN CN201910284654.4A patent/CN111807475A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108301013A (en) * | 2018-02-14 | 2018-07-20 | 中氧科技（广州）有限公司 | A kind of preparation method for the modified anode of lead dioxide generating ozone |
Non-Patent Citations (2)
| Title |
|---|
| 姚莲芳: "Ti/Sb-SnO2/β-PbO2电极制备及其用于水中有机物浓度检测", 《氯碱工业》 * |
| 谭立荣: "电沉积制备PbO2/纳米金刚石复合电极及其电催化性能", 《中国优秀硕士学位论文全文数据库 工程科技Ｉ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477371A (en) * | 2022-09-05 | 2022-12-16 | 湖南新锋科技有限公司 | Diamond-lead oxide doped coupling electrode and preparation method and application thereof |
| CN115477371B (en) * | 2022-09-05 | 2023-12-22 | 湖南新锋科技有限公司 | Doped diamond-lead oxide coupling electrode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105621541A (en) | Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof | |
| WO2018023912A1 (en) | Indium-doped titanium-based lead dioxide electrode, and manufacturing method thereof and application of same | |
| CN105110425A (en) | Preparation method of carbon-nanotube-modified three-dimensional porous-titanium-base lead dioxide electrode | |
| CN107020074A (en) | A kind of electro-catalysis POROUS TITANIUM filter membrane with micro-nano structure and preparation method thereof | |
| CN108217852B (en) | Lead dioxide electrode used as anode in electrocatalytic sewage treatment and preparation method thereof | |
| CN110272100B (en) | Ti4O7Preparation method of ceramic microfiltration membrane electrode of coating | |
| CN104591342A (en) | Preparation method of Ti/Ebonex/PbO2 electrode for sewage deep-treatment | |
| CN102464382B (en) | High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water | |
| CN105239095A (en) | Method for preparing Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode and degrading reactive blue 117 through Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode | |
| CN103981537A (en) | Preparation method and application of Pd/3DOM TiO2/BDD electrode used for photoelectrocatalytic reduction treatment of organic pollutants | |
| CN110803743A (en) | Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode | |
| CN108328703B (en) | Preparation of titanium-based titanium dioxide nanotube deposited tin-antimony-fluorine electrode and application of electrode in chromium-electroplating wastewater chromium fog inhibitor degradation | |
| CN102320683B (en) | Titanium-based tin-antimony-platinum oxide electrode material and preparation method thereof | |
| CN101956194A (en) | Method for preparing TiO2 thin film modified titanium-based beta-PbO2 photoelectrode | |
| CN111807475A (en) | Titanium-based diamond-doped lead dioxide electrode and catalytic degradation technology thereof for bentazon | |
| CN111186883B (en) | Novel preparation technology of lead dioxide electrode modified by titanium tetroxide nanotube | |
| CN110330078B (en) | High-efficiency long-life three-dimensional structure antimony-doped tin oxide electrode | |
| CN107902731B (en) | Nickel-boron-fluorine co-doped lead dioxide anode and preparation method and application thereof | |
| CN109553162A (en) | It is a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation method of electrode | |
| CN102505127A (en) | Preparation method for noble metal modified titanium anode materials | |
| CN105112936A (en) | Preparation method of three-dimensional macroporous-structure PbO2 electrode with high catalysis activity | |
| CN113562815A (en) | Preparation method of composite coating DSA electrode for water treatment and prepared composite coating DSA electrode | |
| CN109052574A (en) | Ti/SnO is prepared based on tricarboxylic organic acids-Sn (II)/Sb (III) complex compound2The method of-Sb electrode | |
| Guan et al. | Improvement of Photocatalytic Performance for the g‐C3N4/MoS2 Composite Used for Hypophosphite Oxidation | |
| CN112429813B (en) | Blue-TiO doped with carbon nano tube 2 /CNT-PbO 2 Preparation method of electrode material |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201023 |