CN107188273A - A kind of preparation method of three-dimensional carbon metal oxides electro catalytic electrode - Google Patents
A kind of preparation method of three-dimensional carbon metal oxides electro catalytic electrode Download PDFInfo
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- CN107188273A CN107188273A CN201710288557.3A CN201710288557A CN107188273A CN 107188273 A CN107188273 A CN 107188273A CN 201710288557 A CN201710288557 A CN 201710288557A CN 107188273 A CN107188273 A CN 107188273A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
Abstract
The invention belongs to the preparation field of electrode material in electrocatalysis high-grade oxidized wastewater treatment, and disclose a kind of preparation method of three-dimensional carbon metal oxides electro catalytic electrode.(a) three-dimensional carbon material is chosen to clean as matrix material, and to it；(b) configuration metal oxide electroplate liquid or maceration extract；(c) the three-dimensional carbon material after cleaning is placed in metal oxide electroplate liquid, under certain temperature and current density, electro-deposition is carried out using three-dimensional carbon material as anode, or the three-dimensional carbon material after cleaning is placed in progress impregnation-calcination process in metal oxide impregnated liquid so as to prepare required three-dimensional carbon metal oxides electro catalytic electrode.By means of the invention it is possible to prepare, chemical property is stable, and specific surface area is big, and the three-dimensional carbon metal oxides electro catalytic electrode more than surface-active site effectively raises wastewater degradation efficiency, reduces energy consumption.
Description
Technical field
The invention belongs to the preparation field of electrode material in electrocatalysis high-grade oxidized wastewater treatment, more particularly, to one
Plant the preparation method of three-dimensional carbon metal oxides electro catalytic electrode.
Background technology
For the processing of industrial wastewater, traditional processing method mainly includes biological treatment, physical-chemical process and height
Level oxidizing process etc..Electrocatalytic Oxidation, as one kind of advanced oxidation processes, is by the electrode material table with electro catalytic activity
Face direct oxidation organic pollution, or the free radical group indirect oxidation with Strong oxdiative ability is produced under electrochemical action
Organic pollution in waste water, the Green Chemical Technology for finally making its degradable is a kind of senior oxygen of current most prospect
Change technology, in electrochemicial oxidation bio-refractory organic wastewater system, electrode material is " core ", high-performance electrode material
The research and development of material are always the research emphasis of electro-chemical water handling process.
Metal oxide electrode is due to factors such as oxygen evolution potential is higher, good catalytic activity, moderate costs, as at present most
The electro catalytic electrode material of tool prospect, has much currently for the study on the modification of metal oxide electrode material, including element is mixed
Miscellaneous, microscopic appearance synthesis, nano material doping etc..Electrode prepared by these method of modifying, is improved in spite of certain performance, but
Still face that electrode life is not high compared with short, current efficiency, energy consumption is more, by mass transfer rate effect is influenceed to the removing of low concentration pollutant
The shortcoming of really poor grade.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of three-dimensional carbon metal oxides electricity
The preparation method of catalysis electrode, is used as matrix material by the three-dimensional carbon material of selection and prepares three-dimensional carbon metal oxides coating electricity
Pole, strengthens the specific surface area of metal oxide electrode, the mass-transfer efficiency during electro-catalysis is improved, so as to improve electrode material
Catalytic performance, and then improve coulombic efficiency, reduction energy consumption, thus solves that matrix is easy to oxidation and wastewater degradation rate is low, high energy consumption
Technical problem.
To achieve the above object, it is proposed, according to the invention, there is provided a kind of system of three-dimensional carbon metal oxides electro catalytic electrode
Preparation Method, it is characterised in that the preparation method comprises the following steps：
(a) selection and pretreatment of matrix material
Three-dimensional carbon material is chosen to clean as matrix material, and to it, wherein, the three-dimensional carbon material be carbon felt,
Carbon cloth, netted vitrescence carbon, one kind in porous carbon or combination；
(b) configuration of electroplate liquid or maceration extract
Metal oxide electroplate liquid or maceration extract are configured, wherein, the metal oxide electroplate liquid is brown lead oxide, described
Metal oxide impregnated liquid is one kind in tin ash, ruthenic oxide, iridium dioxide；
(c) electro-deposition or impregnation-calcination
(c1) when using metal oxide electroplate liquid
The three-dimensional carbon material after cleaning is placed in the electroplate liquid, under certain temperature and current density, by three
Carbon material is tieed up as anode and carries out electro-deposition, so as to prepare required three-dimensional carbon metal oxides electro catalytic electrode.
(c2) when using metal oxide impregnated liquid
The three-dimensional carbon material after cleaning is placed in after being impregnated in the maceration extract and dried, then in inert gas shielding
Lower roasting, repeats the three-dimensional carbon metal oxides electricity needed for the dipping, drying and roasting process are prepared for several times, thus and urges
Polarizing electrode.
It is further preferred that in step (a), the cleaning process is cleaned using water, organic solvent and acid solution, its
In, organic solvent preferred alcohol or acetone, acid solution are preferred to use the mixed liquor of nitric acid and sulfuric acid, and the volume ratio of the two is preferred to use
1~3:1~9.
It is further preferred that in step (b), the plumbi nitras configured using 8.25~16.5g of the electroplate liquid, 0~
2.41g copper nitrates, 0~0.84g sodium fluorides, 0.625~3.125ml concentrated nitric acids are dissolved in deionized water, stirring to its dissolving.
It is further preferred that in step (c1), the temperature of the deposition is preferred to use 40~80 DEG C.
It is further preferred that in step (c1), the current density of the deposition is preferred to use 10~40mA/cm2。
It is further preferred that in step (c2), the sintering temperature is preferred to use 500~700 DEG C.
It is further preferred that in step (c2), the roasting time is preferred to use 0.5~3h.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention from three-dimensional carbon material by being used as matrix material, compared with traditional titanium-based metal oxide electrode,
There is " cracking " in traditional titanium-based metal oxide electrode surface, electrolyte, which can enter coat inside, causes Titanium base to aoxidize, and aoxidizes
Titanium base poorly conductive afterwards, analysis oxygen is serious, and eventually results in coating shedding, three-dimensional carbon materials chemistry property after internal pressure increase
It is stable, oxidative deactivation layer will not be formed；
2nd, the present invention has three-dimensional structure by the three-dimensional carbon metal oxides electrode prepared, is one kind new three
Electrode material is tieed up, compared with classic flat-plate titanium matrix metal oxide electrode, specific surface area is big, and surface-active site is more；
3rd, the present invention has good adsorption capacity by the three-dimensional carbon metal oxides electrode prepared, is conducive to
The effect of absorption-catalytic degradation-absorption is produced, mass-transfer efficiency is improved, strengthens catalytic effect；
4th, the present invention is by using specific depositing temperature and current density, it is ensured that depositing metal oxide active layer
Densification, below or above this temperature range and depositing current density scope, prepared carbon based metal oxide active layer covers
Lid is uneven, and electrode easily lumps, and ultimately results in electrode activity poor；
5th, on the one hand the present invention can ensure that metal oxide has one by using specific sintering temperature and roasting time
Determine crystallinity, on the other hand again the structure of carbon base body in itself will not be made to change, all can below or above this temperature range
Cause final prepared carbon based metal oxide active poor；
6th, the present invention by the three-dimensional carbon metal oxides electrode for preparing in practice effect test, degradation efficiency
Improved a lot compared with classic flat-plate titanium-based metal oxide electrode, in the case of other conditions identical, in 30min, drop
Solution rate reaches more than 95%, and flat board titanium matrix metal oxide electrode reaches that same degradation rate then needs more than 120min.
Brief description of the drawings
Fig. 1 is according to the three-dimensional carbon metal oxides electro catalytic electrode preparation side constructed by the preferred embodiments of the present invention
Method flow chart；
Fig. 2 is according to the carbon felt lead dioxide electrode and ti-supported lead dioxide electric pole constructed by the preferred embodiments of the present invention
The concentration map of material degradation phenol；
Fig. 3 is according to the carbon felt lead dioxide electrode and ti-supported lead dioxide electric pole constructed by the preferred embodiments of the present invention
The degradation efficiency figure of material degradation phenol (initial concentration is 100mg/L).
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below that
Not constituting conflict between this can just be mutually combined.
Fig. 1 is according to the three-dimensional carbon metal oxides electro catalytic electrode preparation side constructed by the preferred embodiments of the present invention
Method flow chart；As shown in figure 1, citing provides a kind of preparation method of three-dimensional carbon base lead dioxide electrode below, mainly include
Following steps：
(a) carbon felt material is pre-processed：Mainly include the steps such as washing, organic solvent cleaning, pickling composition；Water
Wash, mainly carrying out preliminary cleaning to impurity, spot of Carbon felt surface etc. removes；Organic solvent is cleaned, mainly using alcohol
Equal solvent washes away the greasy dirt of Carbon felt surface；Pickling, is mainly soaked using certain density acid solution to carbon felt, to strengthen table
The hydrophily in face；After pickling, then neutrality is washed to, dried, it is standby；
(b) configuration of brown lead oxide electroplate liquid：Mainly include a certain proportion of plumbi nitras, copper nitrate, sodium fluoride, nitric acid,
Using water as solvent, it is mixed evenly to clarification；
(c) during the carbon felt matrix for obtaining the step (a) is placed in the electroplate liquid that the step (b) obtains as anode,
Anode of lead dioxide electro-deposition is carried out under conditions of certain temperature, stirring and certain current density, so as to prepare carbon felt two
Lead dioxide electrode.
As shown in figure 1, citing below provides a kind of preparation method of three-dimensional carbon-based stannic oxide electrode, it is main include with
Lower step：
(a) carbon felt material is pre-processed：Mainly include the steps such as washing, organic solvent cleaning, pickling composition；Water
Wash, mainly carrying out preliminary cleaning to impurity, spot of Carbon felt surface etc. removes；Organic solvent is cleaned, mainly using alcohol
Equal solvent washes away the greasy dirt of Carbon felt surface；Pickling, is mainly soaked using certain density acid solution to carbon felt, to strengthen table
The hydrophily in face；After pickling, then neutrality is washed to, dried, it is standby；
(b) configuration of tin ash maceration extract：Mainly include a certain proportion of five water and butter of tin, trichloride antimony, salt
Acid, using isopropanol as solvent, be mixed evenly to clarification；
(c) the carbon felt matrix that the step (a) obtains is placed in the maceration extract that the step (b) obtains, impregnates several points
Clock, is placed in the tubular type kiln roasting 0.5-3h of inert gas shielding after certain temperature drying, repeats operation above for several times, so that
Prepare carbon felt stannic oxide electrode.
Below with reference to Fig. 1 flow chart, and combine following multiple embodiments specifically to further illustrate the present invention.
Embodiment 1
(1) carbon felt is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon felt that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 60ml nitric acid, 20ml sulfuric acid in beaker respectively, the carbon felt that step 2 is obtained is placed in one, ultrasonic 3h, Zhi Houyong
A large amount of deionized waters rinse carbon felt repeatedly, until flushing liquor pH is neutrality, obtained carbon felt is placed in into dry for standby in baking oven.
(2) 8.25g plumbi nitras (Pb (NO are taken3)2), 2.41g copper nitrates (Cu (NO3)2·3H2O), 0.168g sodium fluorides
(NaF), 3.125ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) carbon felt for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in the electricity of configuration in (2) as negative electrode
Deposition solution.In 60 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 20mA/cm2Current density enter
Row anode lead dioxide deposition, sedimentation time is 60min.It is using deionized water that obtained carbon felt lead dioxide electrode is clear afterwards
Wash clean, dry for standby.
(4) 150ml two, beaker is taken, it is 100mg/L phenol solution and 0.1M nothing that 100mL concentration is added thereto
Aqueous sodium persulfate is used as electrolyte.Ti-supported lead dioxide electric pole respectively to be prepared under carbon felt lead dioxide electrode and the same terms again
As anode, titanium plate is as negative electrode, with identical current density (20mA/cm2) under carry out electrochemical degradation, preceding 30min, every
10min samples 1ml；1ml is sampled per half an hour afterwards.Phenol concentration is determined using high performance liquid chromatography (HPLC) and calculates phenol
Degradation efficiency, then concentration time curve and degradation rate-time graph are drawn, Fig. 2 is according to the preferred embodiments of the present invention institute structure
The carbon felt lead dioxide electrode and the concentration map of ti-supported lead dioxide electric pole material degradation phenol built；Fig. 3 is according to the present invention
(concentration is 100mg/ for carbon felt lead dioxide electrode and ti-supported lead dioxide electric pole material degradation phenol constructed by preferred embodiment
L degradation efficiency figure), as shown in Figures 2 and 3.
Embodiment 2
(1) carbon cloth is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon cloth that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 10ml nitric acid, 90ml sulfuric acid in beaker respectively, the carbon cloth that step 2 is obtained is placed in one, ultrasonic 3h, Zhi Houyong
A large amount of deionized waters rinse carbon cloth repeatedly, until flushing liquor pH is neutrality, obtained carbon cloth is placed in into dry for standby in baking oven.
(2) 16.5g plumbi nitras (Pb (NO are taken3)2), 0g copper nitrates (Cu (NO3)2·3H2O), 0g sodium fluorides (NaF),
0.625ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) carbon cloth for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in the electricity of configuration in (2) as negative electrode
Deposition solution.In 40 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 10mA/cm2Current density enter
Row anode lead dioxide deposition, sedimentation time is 120min.Deionized water is used afterwards by obtained carbon cloth lead dioxide electrode
Clean up, dry for standby.
Embodiment 3
(1) netted vitrescence carbon is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.100ml is placed on to go
In ionized water, ultrasonic 1h, dry for standby；100ml ethanol is taken in beaker, the netted vitrescence carbon that step 1 is obtained is placed in one,
Ultrasonic 2h, dry for standby；40ml nitric acid, 20ml sulfuric acid are taken respectively in beaker, and the netted vitrescence carbon that step 2 is obtained is placed in it
In, ultrasonic 3h rinses netted vitrescence carbon repeatedly with a large amount of deionized waters afterwards, until flushing liquor pH is neutrality, by obtained net
Shape vitrescence carbon is placed in dry for standby in baking oven.
(2) 8.25g plumbi nitras (Pb (NO are taken3)2), 2.41g copper nitrates (Cu (NO3)2·3H2O), 0.14g sodium fluorides
(NaF), 3.125ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) the netted vitrescence carbon for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in (2) and matched somebody with somebody as negative electrode
The electric depositing solution put.In 80 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 40mA/cm2Electric current
Density carries out anode lead dioxide deposition, and sedimentation time is 240min.Afterwards will obtained netted vitrescence carbon using deionized water
Lead dioxide electrode is cleaned up, dry for standby.
Embodiment 4
(1) carbon felt is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon felt that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 60ml nitric acid, 40ml sulfuric acid in beaker respectively, the carbon felt that step 2 is obtained is placed in one, ultrasonic 3h, Zhi Houyong
A large amount of deionized waters rinse carbon felt repeatedly, until flushing liquor pH is neutrality, obtained carbon felt is placed in into dry for standby in baking oven.
(2) 10.5g plumbi nitras (Pb (NO are taken3)2), 1.41g copper nitrates (Cu (NO3)2·3H2O), 0.768g sodium fluorides
(NaF), 3.025ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) carbon felt for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in the electricity of configuration in (2) as negative electrode
Deposition solution.In 80 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 40mA/cm2Current density enter
Row anode lead dioxide deposition, sedimentation time is 240min.Deionized water is used afterwards by obtained carbon felt lead dioxide electrode
Clean up, dry for standby.
Embodiment 5
(1) porous carbon is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionizations
In water, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the porous carbon that step 1 is obtained is placed in one, ultrasonic 2h,
Dry for standby；Take 20ml nitric acid, 80ml sulfuric acid in beaker respectively, the porous carbon that step 2 is obtained is placed in one, ultrasonic 3h,
Porous carbon is rinsed repeatedly with a large amount of deionized waters afterwards, until flushing liquor pH is neutrality, obtained porous carbon is placed in baking oven
Dry for standby.
(2) 15g plumbi nitras (Pb (NO are taken3)2), 2g copper nitrates (Cu (NO3)2·3H2O), 0.84g sodium fluorides (NaF),
0.825ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) porous carbon for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in configuration in (2) as negative electrode
Electric depositing solution.In 80 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 40mA/cm2Current density
Anode lead dioxide deposition is carried out, sedimentation time is 240min.Deionized water is used afterwards by obtained porous carbon brown lead oxide
Electrode clean is clean, dry for standby.
Embodiment 6
(1) carbon felt is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon felt that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 40ml nitric acid, 20ml sulfuric acid in beaker respectively, the carbon felt that step 2 is obtained is placed in one, ultrasonic 3h, Zhi Houyong
A large amount of deionized waters rinse carbon felt repeatedly, until flushing liquor pH is neutrality, obtained carbon felt is placed in into dry for standby in baking oven.
(2) 16.5g plumbi nitras (Pb (NO are taken3)2), 1.5g copper nitrates (Cu (NO3)2·3H2O), 0g sodium fluorides (NaF),
0.625ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) carbon felt for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in the electricity of configuration in (2) as negative electrode
Deposition solution.In 80 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 40mA/cm2Current density enter
Row anode lead dioxide deposition, sedimentation time is 240min.Deionized water is used afterwards by obtained carbon felt lead dioxide electrode
Clean up, dry for standby.
Embodiment 7
(1) carbon felt is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon felt that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 30ml nitric acid, the 30ml concentrated sulfuric acids in beaker respectively, the carbon felt that step 2 is obtained is placed in one, ultrasonic 3h, afterwards
Carbon felt is rinsed repeatedly with a large amount of deionized waters, until flushing liquor pH is neutrality, obtained carbon felt is placed in dry for standby in baking oven.
(2) 8.25g plumbi nitras (Pb (NO are taken3)2), 0g copper nitrates (Cu (NO3)2·3H2O), 0.84g sodium fluorides (NaF),
3.125ml concentrated nitric acid (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) carbon felt for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in the electricity of configuration in (2) as negative electrode
Deposition solution.In 60 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 20mA/cm2Current density enter
Row anode lead dioxide deposition, sedimentation time is 30min.It is using deionized water that obtained carbon felt lead dioxide electrode is clear afterwards
Wash clean, dry for standby.
Embodiment 8
(1) netted vitrescence carbon is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.100ml is placed on to go
In ionized water, ultrasonic 1h, dry for standby；100ml ethanol is taken in beaker, the netted vitrescence carbon that step 1 is obtained is placed in one,
Ultrasonic 2h, dry for standby；60ml nitric acid, 20ml sulfuric acid are taken respectively in beaker, and the netted vitrescence carbon that step 2 is obtained is placed in it
In, ultrasonic 3h rinses netted vitrescence carbon repeatedly with a large amount of deionized waters afterwards, until flushing liquor pH is neutrality, by obtained net
Shape vitrescence carbon is placed in dry for standby in baking oven.
(2) 16.5g plumbi nitras (Pb (NO are taken3)2), 2.41g copper nitrates (Cu (NO3)2·3H2O), 0.84g sodium fluorides
(NaF), 3.125ml concentrated nitric acids (HNO3) be dissolved in 100mL deionized waters, stirring to its dissolving.
(3) the netted vitrescence carbon for obtaining (1) is as anode, and the titanium sheet of similar face product is placed in (2) and matched somebody with somebody as negative electrode
The electric depositing solution put.In 60 DEG C of heating water baths, in the case of stirring, using D.C. regulated power supply, with 20mA/cm2Electric current
Density carries out anode lead dioxide deposition, and sedimentation time is 60min.Deionized water is used afterwards by obtained carbon felt brown lead oxide
Electrode clean is clean, dry for standby.
Embodiment 9
(1) carbon felt is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon felt that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 40ml nitric acid, 20ml sulfuric acid in beaker respectively, the carbon felt that step 2 is obtained is placed in one, ultrasonic 3h, Zhi Houyong
A large amount of deionized waters rinse carbon felt repeatedly, until flushing liquor pH is neutrality, obtained carbon felt is placed in into dry for standby in baking oven.
(2) five water and butter of tin, trichloride antimony, hydrochloric acid is taken to be dissolved in isopropanol, stirring configures maceration extract to its dissolving.
(3) the three-dimensional carbon material of the carbon felt for obtaining (1), which is placed in the metal oxide impregnated liquid, impregnates certain time,
80 DEG C of drying, afterwards under nitrogen protection, 0.5h are calcined in tube furnace at 500 DEG C.Operation more than repeating is for several times so as to make
For the three-dimensional carbon metal oxides electro catalytic electrode needed for going out.
Embodiment 10
(1) carbon cloth is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.It is placed on 100ml deionized waters
In, ultrasonic 1h, dry for standby；Take 100ml ethanol in beaker, the carbon cloth that step 1 is obtained is placed in one, ultrasonic 2h, drying
It is standby；Take 40ml nitric acid, 20ml sulfuric acid in beaker respectively, the carbon cloth that step 2 is obtained is placed in one, ultrasonic 3h, Zhi Houyong
A large amount of deionized waters rinse carbon cloth repeatedly, until flushing liquor pH is neutrality, obtained carbon cloth is placed in into dry for standby in baking oven.
(2) three hydrate ruthenium trichlorides, hydrochloric acid are taken to be dissolved in isopropanol, stirring configures maceration extract to its dissolving.
(3) the three-dimensional carbon material of the carbon cloth for obtaining (1), which is placed in the metal oxide impregnated liquid, impregnates certain time,
150 DEG C of drying, afterwards under nitrogen protection, 3h are calcined in tube furnace at 700 DEG C.Operation more than repeating is for several times so as to prepare
Go out required three-dimensional carbon metal oxides electro catalytic electrode.
Embodiment 11
(1) netted vitrescence carbon is taken, the strip that specification is 5cm*2cm*0.3cm is cut into.100ml is placed on to go
In ionized water, ultrasonic 1h, dry for standby；100ml ethanol is taken in beaker, the netted vitrescence carbon that step 1 is obtained is placed in one,
Ultrasonic 2h, dry for standby；40ml nitric acid, 20ml sulfuric acid are taken respectively in beaker, and the netted vitrescence carbon that step 2 is obtained is placed in it
In, ultrasonic 3h rinses netted vitrescence carbon repeatedly with a large amount of deionized waters afterwards, until flushing liquor pH is neutrality, by obtained net
Shape vitrescence carbon is placed in dry for standby in baking oven；
(2) six chloride hydrate iridium, hydrochloric acid are taken to be dissolved in isopropanol, stirring configures maceration extract to its dissolving.
(3) the three-dimensional carbon material of the netted vitrescence carbon for obtaining (1), which is placed in the metal oxide impregnated liquid, impregnates certain
Time, in 120 DEG C of drying, afterwards under nitrogen protection, 1h is calcined at 600 DEG C in tube furnace.Operation more than repeating is for several times
So as to prepare required three-dimensional carbon metal oxides electro catalytic electrode.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of three-dimensional carbon metal oxides electro catalytic electrode, it is characterised in that under the preparation method includes
Row step：
(a) selection and pretreatment of matrix material
Three-dimensional carbon material is chosen to clean as matrix material, and to it, wherein, the three-dimensional carbon material be carbon felt, carbon cloth,
Netted vitrescence carbon, one kind in porous carbon or combination；
(b) configuration of electroplate liquid or maceration extract
Metal oxide electroplate liquid or maceration extract are configured, wherein, the metal oxide electroplate liquid is brown lead oxide, the metal
Oxide maceration extract is one kind in tin ash, ruthenic oxide, iridium dioxide；
(c) electro-deposition or impregnation-calcination
(c1) when using metal oxide electroplate liquid
The three-dimensional carbon material after cleaning is placed in the electroplate liquid, three-dimensional carbon material electro-deposition is subjected to, so as to prepare
Go out required three-dimensional carbon metal oxides electro catalytic electrode.
(c2) when using metal oxide impregnated liquid
The three-dimensional carbon material after cleaning is placed in after being impregnated in the maceration extract and dried, then roasted under inert gas shielding
Burn, repeat the three-dimensional carbon metal oxides electro-catalysis electricity needed for the dipping, drying and roasting process are prepared for several times, thus
Pole.
2. preparation method as claimed in claim 1, it is characterised in that in step (a), the cleaning process uses water, had
Machine solvent and acid solution are cleaned, wherein, organic solvent preferred alcohol or acetone, acid solution are preferred to use the mixing of nitric acid and sulfuric acid
Liquid, the volume ratio of the two is preferred to use 1~3:1~9.
3. preparation method as claimed in claim 1, it is characterised in that in step (b), the configuration of the electroplate liquid is used
8.25~16.5g plumbi nitras, 0~2.41g copper nitrates, 0~0.84g sodium fluorides, 0.625~3.125ml concentrated nitric acids are dissolved in
In ionized water, stirring to its dissolving.
4. preparation method as claimed in claim 1, it is characterised in that in step (c1), the temperature of the electro-deposition is preferred
Using 40~80 DEG C.
5. preparation method as claimed in claim 1, it is characterised in that in step (c1), the current density of the electro-deposition
It is preferred to use 10~40mA/cm2。
6. preparation method as claimed in claim 1, it is characterised in that in step (c2), the sintering temperature is preferred to use
500~700 DEG C.
7. preparation method as claimed in claim 1, it is characterised in that in step (c2), the roasting time is preferred to use
0.5~3h.
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Application publication date: 20170922 |