CN106277228A - The preparation of a kind of novel high catalytic activity electrode and the research method of Electrocatalysis Degradation methyl blue thereof - Google Patents

The preparation of a kind of novel high catalytic activity electrode and the research method of Electrocatalysis Degradation methyl blue thereof Download PDF

Info

Publication number
CN106277228A
CN106277228A CN201610928852.6A CN201610928852A CN106277228A CN 106277228 A CN106277228 A CN 106277228A CN 201610928852 A CN201610928852 A CN 201610928852A CN 106277228 A CN106277228 A CN 106277228A
Authority
CN
China
Prior art keywords
electrode
tio
sno
deposition
sheet
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.)
Granted
Application number
CN201610928852.6A
Other languages
Chinese (zh)
Other versions
CN106277228B (en
Inventor
徐迈
王凤武
王智成
魏亦军
朱传高
方文彦
王灿永
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huainan Normal University
Original Assignee
Huainan Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huainan Normal University filed Critical Huainan Normal University
Priority to CN201610928852.6A priority Critical patent/CN106277228B/en
Publication of CN106277228A publication Critical patent/CN106277228A/en
Application granted granted Critical
Publication of CN106277228B publication Critical patent/CN106277228B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Abstract

The invention discloses the preparation of a kind of novel high catalytic activity electrode and the research method of Electrocatalysis Degradation methyl blue thereof, belong to electro-catalysis technical field.Electrode is prepared as: anodizing prepares Ti/TiO2NT electrode；At matrix Ti sheet and TiO2Electroplate one layer of Cu bottom NT, then use the method for electro-deposition to coat one layer of SnO on the titania nanotube prepared2Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2Ce, Doping with Rare Earth Lanthanum PbO2The method that the preparation of surface activity layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb (NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulates pH value of solution=3, and electric current density is set to 50～100mA/cm2, electro-deposition 30～60min at 60 DEG C.Electrode stability is good, and during the methyl blue that is used for degrading, catalytic degradation efficiency is high.

Description

The preparation of a kind of novel high catalytic activity electrode and the research of Electrocatalysis Degradation methyl blue thereof Method
Technical field
The invention belongs to electro-catalysis technical field, more particularly, it relates to high catalytic activity Ti/Cu-TiO2NT/SnO2- Ce/La-PbO2Electrode preparation and the research method of Electrocatalysis Degradation methyl blue thereof.
Background technology
Along with society's industrialization degree is more and more higher, environmental pollution that industrialization brings also becomes the sternness that the whole world faces and asks Topic.At present, developing rapidly of chemical industry, pesticide, pharmacy and dyestuff, production process discharges and much environment is had severe contamination Organic pollution.Especially in today that water resource is so deficient, kind and the quantity of industrial discharge pollutant grow with each passing day, and make Limited water resource is by more serious pollution.Scientific investigations showed that, these organic industrial sewages present multicomponent, highly concentrated The features such as degree, molecular structure stabilized, difficult degradation, some also has " three cause " (carcinogenic, teratogenesis, mutagenesis) effect and biological accumulation Property, it is possible to exist for a long time in organism and environment, human health and environment are caused serious threat.Reactive dark blue 194 1 Plant heteroaromatic compound, be used as dyestuff and use, can be used for cotton, viscose fiber dyeing, have preferable dyeability and fastness, It is applicable to various colouring method it can also be used to the printing and dyeing of polyvinyl.But, the waste water containing these water miscible reactive dye is also One of the most intractable waste water, traditional water treatment technology is not fine to these dyestuff treatment effects.
The methods such as traditional physics, chemistry process organic wastewater and there is secondary pollution and high in cost of production problem, so now Research emphasis is few to secondary pollution, low cost and the simple direction of process technique are developed.Although bioanalysis meets this development Requirement, but because it can only degrade biodegradable Organic substance and enjoys limitation.In recent years, high-level oxidation technology was increasingly by state Inside and outside researcher is paid close attention to, and at sewage treatment area, the organic pollution of difficult for biological degradation is had obvious degradation effect.Electrification Learning oxidation technology is a kind of environmentally friendly high-level oxidation technology, can effective degradation biological hardly degraded organic substance, because it has Environmental protection, the advantages such as secondary pollution is few, and safety is high and easy to operate, receive much concern, therefore propose one and can high efficiency drop Solving dyestuff electro-catalytic process is to be badly in need of in prior art solving the technical problem that.Ti/PbO2Electrode is as a kind of electrocatalytic oxidation Anode material, has cheap, good conductivity, good corrosion resistance and catalysis activity advantages of higher, but Ti/PbO2Electrode Activity and stability need to improve further.
Titanium-based titanium dioxide nanotube because having bigger specific surface area, stronger mechanical strength, preferable bio-compatible Property, to biological nontoxic, resistance to acids and bases is good, and good chemical stability, is the most often introduced in PbO2Electrode carries Its catalytic performance high.But Ti/TiO2NT is quasiconductor, simultaneously matrix and TiO2Sometimes in combination with the most firm between NT, cause its electricity Resistance ratio is big, and electrode stability declines, thus current efficiency is the highest during processing sewage, by its conduction of simple electroreduction Property increase rate be not very big, by Ti matrix and and TiO2Layer of metal is electroplated, to improve electrode conductivity between NT And stability, SnO2Have and TiO2And PbO2Close lattice dimensions, easily forms solid solution so that figure layer is relatively tightr, carries The service life of high electrode, and SnO2Gas evolution current potential can be adjusted, thus effectively stop the diffusion of nascent oxygen.But Ti/Cu-TiO2Electro-deposition techniques is used to prepare SnO on NT matrix2-Ce intermediate layer and Doping with Rare Earth Lanthanum Ti matrix PbO2Electrode Prior art is the openest, because Ti/TiO prepared by prior art2NT/PbO2The general specific surface area of electrode is little, and resistance is big, urges Change activity the highest, and electrode corrosion-resistant, stability are the highest, how to improve Ti/TiO2The electric conductivity of NT and stability, and Special process and method prepare surface uniformly, the SnO of the doping vario-property of size tunable2-intermediate layer and rear-earth-doped through TiO2NT repaiies Ti matrix PbO after decorations2Electrode, is another technical problem being badly in need of in prior art solving.
Summary of the invention
1. invention to solve the technical problem that
The problem existed for above-mentioned prior art, one of the technical problem to be solved in the present invention: how to solve matrix and TiO2Sometimes in combination with the most firm between NT, TiO2The big problem of NT resistance, and use special process and method prepare surface uniformly, Size tunable with intermediate layer and surface activity layer and through TiO2Ti matrix PbO after NT modification2Electrode；The invention solves the problems that Technical problem two: how to improve the efficiency of Electrocatalysis Degradation reactive dark blue 194.The invention provides high catalytic activity Ti/ Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode preparation and the research method of Electrocatalysis Degradation reactive dark blue 194 thereof, use direct current The method of current deposits prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, the method is simple to operate, improves sedimentary Purity, density, the uniformity, and reduce its voidage, improve the stability of electrode, with this Ti/Cu-TiO2NT/SnO2-Ce/ La-PbO2Modified electrode is anode, processes reactive dark blue 194 by electrocatalytic oxidation in a cell, the side that this invention provides The efficiency that reactive dark blue 194 is removed in method oxidative degradation is high, electrode good corrosion resistance, degradation process good stability, degradation efficiency ratio Common lead electrode is high, and the degradation rate of methyl blue reaches 99.78%, and the degradation rate of TOC reaches 99.89%, and energy consumption obtains significantly Reduction, energy consumption reduce by 30%, degraded side reaction few, it is ensured that degraded high efficiency, belong to Green Chemistry part.
2. technical scheme
For reaching above-mentioned purpose, the technical scheme that the present invention provides is:
A kind of novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, it is characterised in that first use sun Pole oxidizing process prepares Ti/TiO2NT electrode, wherein, Ti/TiO2NT electrode radius is 125nm, and tube wall is 12nm, passes through electroreduction By Ti4+It is reduced into Ti3+, the Ti/TiO that will reduce2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is reference electricity Pole, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2Electroplate one layer of Cu bottom NT, then use the method for electro-deposition to exist One layer of SnO is coated on the titania nanotube prepared2-Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce(NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, Electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2- Ce, Doping with Rare Earth Lanthanum PbO2The method that the preparation of surface activity layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb(NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulate pH value of solution=2, electric current density be set to 50～ 100mA/cm2, electro-deposition 30～60min at 60 DEG C.
As a further improvement on the present invention, what it was prepared concretely comprises the following steps:
Step one,
Selection pure titanium metal is as titanium sheet, first by titanium sheet successively with 600 mesh, 1000 mesh and three kinds of different sizes of 2000 mesh Sand paper polish, the titanium sheet supersound washing 10min in dehydrated alcohol, acetone, deionized water successively that then will polish, Place into polishing 10min in the mixed solution of ethylene glycol, Fluohydric acid. and redistilled water, and clean with deionized water dry Only, wherein: Fluohydric acid., ethylene glycol is 1:3:10 with the volume ratio of redistilled water；
Step 2,
Use anodizing to prepare titania nanotube, be 0.5%NH at mass fraction under room temperature4F and 2V%H2O Ethylene glycol electrolyte in, make anode with titanium sheet, Cu sheet carries out anodic oxidation as negative electrode, and oxidation voltage is 60V, oxidization time 7h, oxidizing process carries out magnetic agitation all the time, and oxidation uses soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning after terminating 10min, makes annealing treatment under air atmosphere, annealing temperature 500 DEG C, is incubated 2h, and heating-cooling speed is all 2 DEG C/min, can prepare half Footpath is 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3,
The Ti/TiO that step 2 is prepared2NT electrode is as negative electrode, and Pt sheet is as anode, and saturated KCl electrode is as ginseng Ratio electrode, puts into 1mol L-1(NH4)2SO4In solution under-1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；By reduced Ti/TiO2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；? Matrix Ti sheet and TiO2One layer of Cu is electroplated bottom NT.
Step 4, the method for employing electro-deposition coat one layer of SnO on the titania nanotube prepared2In the middle of-Ce Layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed on 500 after room temperature electro-deposition 30min DEG C Muffle furnace is calcined 60min, obtains intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5, the modified electrode deposition surface active layer in coating intermediate layer step 4 prepared, rare earth Pr adulterates PbO2The method that the preparation of surface activity layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb (NO3)2, 0.01～ 0.05M La(NO3)3·6H2O and 0.04M NaF, regulates pH value of solution=2, and electric current density is set to 50～100mA/cm2, in 60 DEG C Lower deposition 30～60min prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
As a further improvement on the present invention, the Ti/TiO that will reduce in preparation method step 32NT electrode is anode, Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2Bottom NT Electroplate one layer of Cu.
As a further improvement on the present invention, preparation method step 4 use the method for electro-deposition at the dioxy prepared Change and on titanium nanotube, coat one layer of SnO2-Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2-Ce, heating and cooling Speed is all 5 DEG C/min；
The high catalytic activity Ti/Cu-TiO of the present invention2NT/SnO2-Ce/La-PbO2Electrode preparation and Electrocatalysis Degradation first thereof The research method that base is blue, the steps include:
1) high catalytic activity Ti/Cu-TiO, is prepared2NT/SnO2-Ce/La-PbO2Electrode
Anodizing is first used to prepare Ti/TiO2NT electrode, wherein, Ti/TiO2NT electrode radius is 125nm, and tube wall is 12nm, Ti4+It is reduced into Ti3+；The Ti/TiO that will have reduced2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is ginseng Ratio electrode, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2Electroplate one layer of Cu bottom NT, then use the side of electro-deposition Method coats one layer of SnO on the titania nanotube prepared2-Ce intermediate layer, deposition liquid component component is 18gSnCl4· 5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, the ethanol that 2mlHCl (37%) is dissolved in 100ml is molten In liquid, electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2-Ce, Doping with Rare Earth Lanthanum PbO2Surface activity layer preparation use DC electrodeposition method, deposition liquid component be 0.1～ 0.5M Pb(NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulates pH value of solution=2, and electric current density is set to 50～100mA/cm2, electro-deposition 30～60min at 60 DEG C.
2), Electrocatalysis Degradation reactive dark blue 194
By the modified Ti/Cu-TiO of preparation in step one2NT/SnO2-Ce/La-PbO2Electrode is made as anode, copper electrode For negative electrode, use constant voltage supply, temperature 25 DEG C, electric current density 70mA/cm2, degradation solution is: 50mg/L reactive dark blue 194+ 0.5mol/LNa2SO4。
As a further improvement on the present invention, step 1) in prepare high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La- PbO2Concretely comprising the following steps of electrode:
Step one,
Selection pure titanium metal is as titanium sheet, first by titanium sheet successively with 600 mesh, 1000 mesh and three kinds of different sizes of 2000 mesh Sand paper polish, the titanium sheet supersound washing 10min in dehydrated alcohol, acetone, deionized water successively that then will polish, Place into polishing 10min in the mixed solution of ethylene glycol, Fluohydric acid. and redistilled water, and clean with deionized water dry Only, wherein: Fluohydric acid., ethylene glycol is 1:3:10 with the volume ratio of redistilled water；
Step 2,
Use anodizing to prepare titania nanotube, be 0.5%NH at mass fraction under room temperature4F and 2V%H2O Ethylene glycol electrolyte in, make anode with titanium sheet, Cu sheet carries out anodic oxidation as negative electrode, and oxidation voltage is 60V, oxidization time 7h, oxidizing process carries out magnetic agitation all the time, and oxidation uses soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning after terminating 10min, makes annealing treatment under air atmosphere, annealing temperature 500 DEG C, is incubated 2h, and heating-cooling speed is all 2 DEG C/min, can prepare half Footpath is 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3,
The Ti/TiO that step 2 is prepared2NT electrode is as negative electrode, and Pt sheet is as anode, and saturated KCl electrode is as ginseng Ratio electrode, puts into 1mol L-1(NH4)2SO4In solution under-1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；By reduced Ti/TiO2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；? Matrix Ti sheet and TiO2One layer of Cu is electroplated bottom NT.
Step 4, the method for employing electro-deposition coat one layer of SnO on the titania nanotube prepared2In the middle of-Ce Layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed on 500 after room temperature electro-deposition 30min DEG C Muffle furnace is calcined 60min, obtains intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5, the modified electrode deposition surface active layer in coating intermediate layer step 4 prepared, rare earth Pr adulterates PbO2The method that the preparation of surface activity layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb (NO3)2, 0.01～ 0.05M La(NO3)3·6H2O and 0.04M NaF, regulates pH value of solution=2, and electric current density is set to 50～100mA/cm2, in 60 DEG C Lower deposition 30～60min prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
As a further improvement on the present invention, the Ti/TiO that will reduce in preparation method step 32NT electrode is anode, Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2Bottom NT Electroplate one layer of Cu.
As a further improvement on the present invention, preparation method step 4 use the method for electro-deposition at the dioxy prepared Change and on titanium nanotube, coat one layer of SnO2-Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2-Ce, heating and cooling Speed is all 5 DEG C/min.
3. beneficial effect
Use the technical scheme that the present invention provides, compared with existing known technology, there is following remarkable result:
(1) one of the present invention novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode, uses sun The method of pole oxidation prepares TiO2NT on titanium sheet matrix, and compared to titanium sheet, its specific surface area significantly increases, it is provided that more sink Plot point.
(2) one of the present invention novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode, by electricity Plating Cu, solves between matrix and TiO2NT sometimes in combination with the most firm, the big problem of TiO2NT resistance.
(3) one of the present invention novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode, uses electricity The method of deposition coats one layer of SnO2-Ce intermediate layer on the titania nanotube prepared so that coating is more tight, carries The service life of high electrode.
(4) preparation of high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode and the electro-catalysis thereof of the present invention is dropped Solve the research method of reactive dark blue 194, electrode prepare simple, simple to operate, equipment is easy to get, technological process is simple, cost of investment Low, the efficiency height of reactive dark blue 194 is removed in the method oxidative degradation that this invention provides, and electrode good corrosion resistance, degradation process is steady Qualitative good, degradation efficiency is higher than common lead electrode, and the degradation rate of reactive dark blue 194 reaches 99.78%, and the degradation rate of TOC reaches 99.89%, energy consumption is significantly reduced, and energy consumption reduces by 30%, and degraded side reaction is few, it is ensured that degraded high efficiency, belongs to Green Chemistry part.
Detailed description of the invention
For further appreciating that present disclosure, below in conjunction with embodiment, the invention will be further described.
For further appreciating that present disclosure, the present invention is described in detail in conjunction with the embodiments.
Embodiment 1
The high catalytic activity Ti/TiO2NT/SnO2-Y/Pr-PbO2 electrode preparation of the present embodiment and Electrocatalysis Degradation thereof are lived The research method of property dark blue 194, its concrete step is as follows:
Step one,
Selection pure titanium metal is as titanium sheet, first by titanium sheet successively with 600 mesh, 1000 mesh and three kinds of different sizes of 2000 mesh Sand paper polish, the titanium sheet supersound washing 10min in dehydrated alcohol, acetone, deionized water successively that then will polish, Place into polishing 10min in the mixed solution of ethylene glycol, Fluohydric acid. and redistilled water, and clean with deionized water dry Only, wherein: Fluohydric acid., ethylene glycol is 1:3:10 with the volume ratio of redistilled water；
Step 2,
Use anodizing to prepare titania nanotube, be 0.5%NH4F and 2V%H2O at mass fraction under room temperature Ethylene glycol electrolyte in, make anode with titanium sheet, Cu sheet carries out anodic oxidation as negative electrode, and oxidation voltage is 60V, oxidization time 7h, oxidizing process carries out magnetic agitation all the time, and oxidation uses soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning after terminating 10min, makes annealing treatment under air atmosphere, annealing temperature 500 DEG C, is incubated 2h, and heating-cooling speed is all 2 DEG C/min, can prepare half Footpath is 125nm, the Ti/TiO2NT electrode of tube wall 12nm；
Step 3,
Ti/TiO2NT electrode step 2 prepared is as negative electrode, and Pt sheet is as anode, and saturated KCl electrode is as ginseng Ratio electrode, puts in 1mol L-1 (NH4) 2SO4 solution reductase 12 0s under-1.5V, Ti4+ is reduced into Ti3+；By reduction well Ti/TiO2NT electrode be anode, Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts in 10mMCuSO4 electroplate liquid； One layer of Cu is electroplated bottom matrix Ti sheet with TiO2NT.
Step 4, the method for employing electro-deposition coat in the middle of one layer of SnO2-Ce on the titania nanotube prepared Layer, deposition liquid component component is 18gSnCl4 5H2O and 0.7g Ce (NO3) 3 6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed on 500 after room temperature electro-deposition 30min Calcining 60min in DEG C Muffle furnace, obtain intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5, the modified electrode deposition surface active layer in coating intermediate layer step 4 prepared, rare earth Pr adulterates The method that the preparation of PbO2 surface activity layer uses DC electrodeposition, deposition liquid component is 0.3M Pb (NO3) 2,0.01M La (NO3) 3 6H2O and 0.04M NaF, regulates pH value of solution=2, and electric current density is set to 50mA/cm2, deposits 50min at 60 DEG C Preparation Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode；
Step 6, using modified for step 5 good electrode as anode, copper electrode, as negative electrode, uses HYL-A type constant current permanent Voltage source, temperature 25 DEG C, electric current density 70mA/cm2, degradation solution is: 50mg/L reactive dark blue 194,0.5mol/L Na2SO4, In electrolytic process, current utilization efficiency is up to 92.5%, and the degradation rate of reactive dark blue 194 reaches 99.6%, and the degradation rate of TOC reaches To 99.5%.
Embodiment 2
The high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode preparation of the present embodiment and electro-catalysis fall thereof Solving the research method of reactive dark blue 194, its process is substantially with embodiment 1, and difference is:
Step one,
Selection pure titanium metal is as titanium sheet, first by titanium sheet successively with 600 mesh, 1000 mesh and three kinds of different sizes of 2000 mesh Sand paper polish, the titanium sheet supersound washing 10min in dehydrated alcohol, acetone, deionized water successively that then will polish, Place into polishing 10min in the mixed solution of ethylene glycol, Fluohydric acid. and redistilled water, and clean with deionized water dry Only, wherein: Fluohydric acid., ethylene glycol is 1:3:10 with the volume ratio of redistilled water；
Step 2,
Use anodizing to prepare titania nanotube, be 0.5%NH4F and 2V%H2O at mass fraction under room temperature Ethylene glycol electrolyte in, make anode with titanium sheet, Cu sheet carries out anodic oxidation as negative electrode, and oxidation voltage is 60V, oxidization time 7h, oxidizing process carries out magnetic agitation all the time, and oxidation uses soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning after terminating 10min, makes annealing treatment under air atmosphere, annealing temperature 500 DEG C, is incubated 2h, and heating-cooling speed is all 2 DEG C/min, can prepare half Footpath is 125nm, the Ti/TiO2NT electrode of tube wall 12nm；
Step 3,
Ti/TiO2NT electrode step 2 prepared is as negative electrode, and Pt sheet is as anode, and saturated KCl electrode is as ginseng Ratio electrode, puts in 1mol L-1 (NH4) 2SO4 solution reductase 12 0s under-1.5V, Ti4+ is reduced into Ti3+；By reduction well Ti/TiO2NT electrode be anode, Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts in 10mMCuSO4 electroplate liquid； One layer of Cu is electroplated bottom matrix Ti sheet with TiO2NT.
Step 4, the method for employing electro-deposition coat in the middle of one layer of SnO2-Ce on the titania nanotube prepared Layer, deposition liquid component component is 18gSnCl4 5H2O and 0.7g Ce (NO3) 3 6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed on 500 after room temperature electro-deposition 30min Calcining 60min in DEG C Muffle furnace, obtain intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5, the modified electrode deposition surface active layer in coating intermediate layer step 4 prepared, rare earth Pr adulterates The method that the preparation of PbO2 surface activity layer uses DC electrodeposition, deposition liquid component is 0.5M Pb (NO3) 2,0.05M La (NO3) 3 6H2O and 0.04M NaF, regulates pH value of solution=3, and electric current density is set to 100mA/cm2, deposits 40min at 60 DEG C Preparation Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 electrode；
Step 6, using modified for step 5 good electrode as anode, copper electrode, as negative electrode, uses HYL-A type constant current permanent Voltage source, temperature 25 DEG C, electric current density 70mA/cm2, degradation solution is: 50mg/L reactive dark blue 194,0.5mol/L Na2SO4, In electrolytic process, current utilization efficiency is up to 93.4%, and the degradation rate of reactive dark blue 194 reaches 99.7%, and the degradation rate of TOC reaches To 99.8%.
The one novel high catalytic activity Ti/TiO2NT/SnO2-Y/Pr-PbO2 electrode of the present embodiment invention, intermediate layer SnO2 has the lattice dimensions close with TiO2 and PbO2, easily forms solid solution so that figure layer is relatively tightr, improves electrode Service life, and SnO2 can adjust gas evolution current potential, thus effectively stop the diffusion of nascent oxygen.In in surface activity layer By the doping of rare earth Pr, making the lattice dilatation of PbO2, granule diminishes, and specific surface increases, and improves more electron transfer and lives Property position, solve the uppity difficult problem of its granule-morphology in prior art, compared with pure PbO2, electro-catalysis position increase, activity Strengthen, be the electrode of a kind of high activity height catalytic efficiency
Employing Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 modified electrode electrocatalytic oxidation in embodiment 1～2 processes The research method of methyl blue, uses the high activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2 of homemade doping vario-property to modify electricity Pole is as anode, and in degradation process, electrode should not inactivate, electrode good corrosion resistance, and electrolytic process selectivity is good, is electrolysed side reaction Few, degradation efficiency is high, and reaction condition is gentle, it is not necessary to add catalyst, and simple to operate, equipment is easy to get, technological process simple, throwing Money low cost, prepares green with degradation process, pollution-free.The efficiency removing methyl blue is high, electrode good corrosion resistance, degradation process Good stability, degradation efficiency is higher than common lead electrode, and the degradation rate of reactive dark blue 194 reaches 99.78%, and the degradation rate of TOC reaches To 99.89%, energy consumption is significantly reduced, and energy consumption reduces by 30%.
Schematically being described the present invention and embodiment thereof above, this description does not has restricted, in embodiment Shown is also one of embodiments of the present invention, and actual structure is not limited thereto.So, if this area is common Technical staff is enlightened by it, in the case of without departing from the invention objective, designs and this technical side without creative Frame mode that case is similar and embodiment, all should belong to protection scope of the present invention.

Claims (10)

1. a novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, it is characterised in that first use anode Oxidizing process prepares Ti/TiO2NT electrode, wherein, Ti/TiO2NT electrode radius is 125nm, and tube wall is 12nm, will by electroreduction Ti4+It is reduced into Ti3+, the Ti/TiO that will reduce2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, Put into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2Electroplate one layer of Cu bottom NT, then use the method for electro-deposition in system One layer of SnO is coated on the titania nanotube got ready2-Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce(NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, Electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2- Ce, Doping with Rare Earth Lanthanum PbO2The method that the preparation of surface activity layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb(NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulate pH value of solution=2, electric current density be set to 50～ 100mA/cm2, electro-deposition 30～60min at 60 DEG C.
One the most according to claim 1 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, its Concretely comprising the following steps of preparation:
Step one,
Selection pure titanium metal is as titanium sheet, first by titanium sheet successively with 600 mesh, 1000 mesh and the sand of 2,000 three kinds of different sizes of mesh Paper is polished, the titanium sheet supersound washing 10min in dehydrated alcohol, acetone, deionized water successively that then will polish, then puts Enter polishing 10min in the mixed solution of ethylene glycol, Fluohydric acid. and redistilled water, and clean up with deionized water, its In: Fluohydric acid., ethylene glycol is 1:3:10 with the volume ratio of redistilled water；
Step 2,
Use anodizing to prepare titania nanotube, be 0.5%NH at mass fraction under room temperature4F and 2V%H2The second of O In glycol electrolyte, making anode with titanium sheet, Cu sheet carries out anodic oxidation as negative electrode, and oxidation voltage is 60V, oxidization time 7h, oxygen Change process carries out magnetic agitation all the time, and oxidation uses soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning 10min after terminating, Making annealing treatment under air atmosphere, annealing temperature 500 DEG C, be incubated 2h, heating-cooling speed is all 2 DEG C/min, can prepare radius and be 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3,
The Ti/TiO that step 2 is prepared2NT electrode is as negative electrode, and Pt sheet is as anode, and saturated KCl electrode is as reference electricity Pole, puts into 1mol L-1(NH4)2SO4In solution under-1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；The Ti/ that will have reduced TiO2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2One layer of Cu is electroplated bottom NT.
Step 4, the method for employing electro-deposition coat one layer of SnO on the titania nanotube prepared2-Ce intermediate layer, heavy Hydrops component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) it is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；500 DEG C of Muffles it are placed on after room temperature electro-deposition 30min Stove is calcined 60min, obtains intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5, the modified electrode deposition surface active layer in coating intermediate layer step 4 prepared, rare earth Pr adulterates PbO2Surface The method that the preparation of active layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb (NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulates pH value of solution=2, and electric current density is set to 50～100mA/cm2, at 60 DEG C, deposit 30 ～60min prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
One the most according to claim 2 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, its It is characterised by: in preparation method step one, pure titanium metal uses TA1The pure titanium metal of type, its purity is 99.9%.
One the most according to claim 3 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, its It is characterised by: the Ti/TiO that will reduce in preparation method step 32NT electrode is anode, and Pt sheet is negative electrode, saturated KCl electrode For reference electrode, put into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2One layer of Cu is electroplated bottom NT.
One the most according to claim 4 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode, its It is characterised by: preparation method step 4 uses the method for electro-deposition coat one layer on the titania nanotube prepared SnO2-Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecyl Benzene sulfonic acid sodium salt, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；Room temperature electro-deposition 30min After be placed in 500 DEG C of Muffle furnaces calcining 60min, obtain intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min.
6. a novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode Electrocatalysis Degradation reactive dark blue 194 Method, the steps include:
1) high catalytic activity Ti/Cu-TiO, is prepared2NT/SnO2-Ce/La-PbO2Electrode
Anodizing is first used to prepare Ti/TiO2NT electrode, wherein, Ti/TiO2NT electrode radius is 125nm, and tube wall is 12nm, by electroreduction by Ti4+It is reduced into Ti3+, the Ti/TiO that will reduce2NT electrode is anode, and Pt sheet is negative electrode, saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2Electroplate one layer of Cu bottom NT, then adopt On the titania nanotube prepared, one layer of SnO is coated by the method for electro-deposition2-Ce intermediate layer, deposits liquid component component For 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in In the ethanol solution of 100ml, electric current density 20mA/cm2；Calcining it is placed in 500 DEG C of Muffle furnaces after room temperature electro-deposition 30min 60min, obtains intermediate layer SnO2-Ce, Doping with Rare Earth Lanthanum PbO2The method that the preparation of surface activity layer uses DC electrodeposition, heavy Hydrops component is 0.1～0.5M Pb (NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulation pH value of solution= 3, electric current density is set to 50～100mA/cm2, at 60 DEG C, Ti/Cu-TiO is prepared in electro-deposition 30～60min2NT/SnO2-Ce/ La-PbO2Electrode；
2), Electrocatalysis Degradation reactive dark blue 194
By the modified Ti/Cu-TiO of preparation in step one2NT/SnO2-Ce/La-PbO2Electrode is as anode, and copper electrode is as the moon Pole, uses constant voltage supply, temperature 25 DEG C, electric current density 70mA/cm2, degradation solution is: 50mg/L reactive dark blue 194+ 0.5mol/LNa2SO4, regulate pH value of solution=6.
One the most according to claim 6 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode electricity The method of catalytic degradation methyl blue, it is characterised in that: step 1) in prepare high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La- PbO2Concretely comprising the following steps of electrode:
Step one,
Selection pure titanium metal is as titanium sheet, first by titanium sheet successively with 600 mesh, 1000 mesh and the sand of 2,000 three kinds of different sizes of mesh Paper is polished, the titanium sheet supersound washing 10min in dehydrated alcohol, acetone, deionized water successively that then will polish, then puts Enter polishing 10min in the mixed solution of ethylene glycol, Fluohydric acid. and redistilled water, and clean up with deionized water, its In: Fluohydric acid., ethylene glycol is 1:3:10 with the volume ratio of redistilled water；
Step 2,
Use anodizing to prepare titania nanotube, be 0.5%NH at mass fraction under room temperature4F and 2V%H2The second of O In glycol electrolyte, making anode with titanium sheet, Cu sheet carries out anodic oxidation as negative electrode, and oxidation voltage is 60V, oxidization time 7h, oxygen Change process carries out magnetic agitation all the time, and oxidation uses soaked in absolute ethyl alcohol sample 2h, dehydrated alcohol ultrasonic cleaning 10min after terminating, Making annealing treatment under air atmosphere, annealing temperature 500 DEG C, be incubated 2h, heating-cooling speed is all 2 DEG C/min, can prepare radius and be 125nm, the Ti/TiO of tube wall 12nm2NT electrode；
Step 3,
The Ti/TiO that step 2 is prepared2NT electrode is as negative electrode, and Pt sheet is as anode, and saturated KCl electrode is as reference electricity Pole, puts into 1mol L-1(NH4)2SO4In solution under-1.5V reductase 12 0s, Ti4+It is reduced into Ti3+；The Ti/ that will have reduced TiO2NT electrode is anode, and Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；At matrix Ti sheet and TiO2One layer of Cu is electroplated bottom NT.
Step 4, the method for employing electro-deposition coat one layer of SnO on the titania nanotube prepared2-Ce intermediate layer, heavy Hydrops component component is 18gSnCl4·5H2O and 0.7g Ce (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) it is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；500 DEG C of Muffles it are placed on after room temperature electro-deposition 30min Stove is calcined 60min, obtains intermediate layer SnO2-Ce, temperature rate is all 5 DEG C/min；
Step 5, the modified electrode deposition surface active layer in coating intermediate layer step 4 prepared, rare earth Pr adulterates PbO2Surface The method that the preparation of active layer uses DC electrodeposition, deposition liquid component is 0.1～0.5M Pb (NO3)2, 0.01～0.05M La (NO3)3·6H2O and 0.04M NaF, regulates pH value of solution=2, and electric current density is set to 50～100mA/cm2, at 60 DEG C, deposit 30 ～60min prepares Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode.
One the most according to claim 7 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode electricity The method of catalytic degradation activity dark blue 194, it is characterised in that: in preparation method step one, pure titanium metal uses TA1The pure titanium of type Metal, its purity is 99.9%.
One the most according to claim 8 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode electricity The method of catalytic degradation activity dark blue 194, it is characterised in that: the Ti/TiO that will reduce in preparation method step 32NT electrode For anode, Pt sheet is negative electrode, and saturated KCl electrode is reference electrode, puts into 10mMCuSO4In electroplate liquid；Matrix Ti sheet with TiO2One layer of Cu is electroplated bottom NT..
One the most according to claim 9 novel high catalytic activity Ti/Cu-TiO2NT/SnO2-Ce/La-PbO2Electrode electricity The method of catalytic degradation activity dark blue 194, it is characterised in that: preparation method step 4 use the method for electro-deposition preparing Titania nanotube on coat one layer of SnO2-Ce intermediate layer, deposition liquid component component is 18gSnCl4·5H2O and 0.7gCe (NO3)3·6H2O, 0.1g dodecylbenzene sodium sulfonate, 2mlHCl (37%) is dissolved in the ethanol solution of 100ml, electric current density 20mA/cm2；It is placed in 500 DEG C of Muffle furnaces calcining 60min after room temperature electro-deposition 30min, obtains intermediate layer SnO2-Ce, heating and cooling Speed is all 5 DEG C/min.
CN201610928852.6A 2016-10-31 2016-10-31 A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue Active CN106277228B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610928852.6A CN106277228B (en) 2016-10-31 2016-10-31 A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610928852.6A CN106277228B (en) 2016-10-31 2016-10-31 A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue

Publications (2)

Publication Number Publication Date
CN106277228A true CN106277228A (en) 2017-01-04
CN106277228B CN106277228B (en) 2019-06-07

Family

ID=57719073

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610928852.6A Active CN106277228B (en) 2016-10-31 2016-10-31 A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue

Country Status (1)

Country Link
CN (1) CN106277228B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108048867A (en) * 2017-12-05 2018-05-18 淮南师范学院 A kind of preparation method of novel photoelectric catalysis material electrode
CN108793339A (en) * 2018-06-08 2018-11-13 淮南师范学院 A kind of novel high catalytic activity electrode prepares and its method of Electrocatalysis Degradation o-chlorphenol
CN110104739A (en) * 2019-05-27 2019-08-09 中国华能集团清洁能源技术研究院有限公司 One kind is for handling industrial circulating cooling water high-efficient electrode and preparation method thereof
CN113061955A (en) * 2021-03-17 2021-07-02 宜兴禹博治环保科技有限公司 Preparation method of conductive polyaniline modified electrode
CN114242981A (en) * 2021-12-17 2022-03-25 太原理工大学 TiO 22-SnO2Composite material and preparation method and application thereof
CN114574896A (en) * 2022-03-18 2022-06-03 南京师范大学 Carbon cloth loaded Ce-CoO oxygen evolution electrocatalyst and preparation method thereof
WO2023208617A3 (en) * 2022-04-28 2024-04-11 Smoltek Ab Nanostructured anode for a water electrolyzer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100147684A1 (en) * 2008-12-12 2010-06-17 Electronics And Telecommunications Research Institute Ultra-sensitive gas sensor using oxide semiconductor nanofiber and method of fabricating the same
CN103436910A (en) * 2013-08-02 2013-12-11 天津工业大学 Preparation method of gluconic acid and glucaric acid
CN105195161A (en) * 2015-09-30 2015-12-30 淮南师范学院 Ti/TiO2NT/Yb-Fe2O3-PbO2 electrode and method for degrading paraquat through electro-catalysis
CN105239095A (en) * 2015-09-30 2016-01-13 淮南师范学院 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100147684A1 (en) * 2008-12-12 2010-06-17 Electronics And Telecommunications Research Institute Ultra-sensitive gas sensor using oxide semiconductor nanofiber and method of fabricating the same
CN103436910A (en) * 2013-08-02 2013-12-11 天津工业大学 Preparation method of gluconic acid and glucaric acid
CN105195161A (en) * 2015-09-30 2015-12-30 淮南师范学院 Ti/TiO2NT/Yb-Fe2O3-PbO2 electrode and method for degrading paraquat through electro-catalysis
CN105239095A (en) * 2015-09-30 2016-01-13 淮南师范学院 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

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108048867A (en) * 2017-12-05 2018-05-18 淮南师范学院 A kind of preparation method of novel photoelectric catalysis material electrode
CN108048867B (en) * 2017-12-05 2019-06-11 淮南师范学院 A kind of preparation method of photoelectrocatalysimaterial material electrode
CN108793339A (en) * 2018-06-08 2018-11-13 淮南师范学院 A kind of novel high catalytic activity electrode prepares and its method of Electrocatalysis Degradation o-chlorphenol
CN110104739A (en) * 2019-05-27 2019-08-09 中国华能集团清洁能源技术研究院有限公司 One kind is for handling industrial circulating cooling water high-efficient electrode and preparation method thereof
CN110104739B (en) * 2019-05-27 2022-02-11 中国华能集团清洁能源技术研究院有限公司 Efficient electrode for treating industrial circulating cooling water and preparation method thereof
CN113061955A (en) * 2021-03-17 2021-07-02 宜兴禹博治环保科技有限公司 Preparation method of conductive polyaniline modified electrode
CN113061955B (en) * 2021-03-17 2023-02-21 宜兴禹博治环保科技有限公司 Preparation method of conductive polyaniline modified electrode
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
CN114574896A (en) * 2022-03-18 2022-06-03 南京师范大学 Carbon cloth loaded Ce-CoO oxygen evolution electrocatalyst and preparation method thereof
CN114574896B (en) * 2022-03-18 2023-01-31 南京师范大学 Carbon cloth loaded Ce-CoO oxygen evolution electrocatalyst and preparation method thereof
WO2023208617A3 (en) * 2022-04-28 2024-04-11 Smoltek Ab Nanostructured anode for a water electrolyzer

Also Published As

Publication number Publication date
CN106277228B (en) 2019-06-07

Similar Documents

Publication Publication Date Title
CN106277228A (en) The preparation of a kind of novel high catalytic activity electrode and the research method of Electrocatalysis Degradation methyl blue thereof
CN109896598B (en) Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water
CN106277229B (en) A kind of method of modified electrode electrocatalytic oxidation processing organic pollutant Atrazine
CN103409778B (en) The TiO2/Cu2O nano heterojunction that compound mask legal system is standby
CN108439553B (en) Electrochemical oxidation device for removing chloride ions in water
CN106630038B (en) Efficient nested electrochemical oxidation multilayer tubular reactor
CN108423776A (en) A kind of method that removing heavy metals and organic matter are removed in capacitive deionization coupling electro-catalysis collaboration
CN108793339A (en) A kind of novel high catalytic activity electrode prepares and its method of Electrocatalysis Degradation o-chlorphenol
CN102092820A (en) Method and device for removing organic matters from water by using double-pool double-effect visible light in response to photo-electro-Fenton reaction
CN102350228A (en) Nano loaded titanium-based electric catalytic film and preparation method thereof
CN108017120A (en) A kind of method using Novel anode electrocatalytic oxidation processing phenol organic wastewater
CN104480493B (en) Method for recycling copper and cadmium and preparing cadmium bronze precursor employing compact biological electrochemical reactor
CN104386785A (en) Preparation method for molybdenum-antimony co-doped titanium-based stannic oxide electrocatalysis electrode
CN113716658B (en) Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure
CN102826630A (en) Application of Bi/TiO2 nanotube array to photocatalytic degradation of sugar manufacturing wastewater
CN206244476U (en) A kind of tin dioxide coating on titanium antimony sub-micron post electrode
CN101956194A (en) Method for preparing TiO2 thin film modified titanium-based beta-PbO2 photoelectrode
CN110980890A (en) Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof
CN102660765A (en) Chemical preparation method of novel porous titanium
CN107841777B (en) A kind of preparation method of witch culture Nano tube array of titanium dioxide
CN104495989B (en) A kind of Electrochemical oxidation device producing waste water for advanced treating amidoximeization
CN108273486B (en) Carbon nano tube/secondary anode oxidized TiO2Nanotube photocatalyst material and preparation method and application thereof
CN112520819B (en) Bismuth-system three-dimensional microsphere heterojunction photoelectrode and preparation and application thereof
CN102614877B (en) Preparation method of transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst
CN105112936B (en) A kind of three-dimensional macroporous structure PbO with high catalytic activity2The preparation method of electrode

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant