CN107245749A - A kind of method and application that sulfur doping out-phase fenton catalyst is prepared in titanium alloy surface - Google Patents
A kind of method and application that sulfur doping out-phase fenton catalyst is prepared in titanium alloy surface Download PDFInfo
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- CN107245749A CN107245749A CN201710436776.1A CN201710436776A CN107245749A CN 107245749 A CN107245749 A CN 107245749A CN 201710436776 A CN201710436776 A CN 201710436776A CN 107245749 A CN107245749 A CN 107245749A
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
A kind of method and application that sulfur doping out-phase fenton catalyst is prepared in titanium alloy surface, it is related to a kind of out-phase fenton catalyst and application.It is long the invention aims to solve the existing homogeneous fenton catalyst reaction time, the applicable pH narrow ranges of Fenton's reaction system, catalyst can not reclaim and class fenton catalyst film layer poor mechanical property the problem of.The content of the invention：First, titanium alloy surface is pre-processed；2nd, electrolyte is prepared；3rd, differential arc oxidation reacts, and obtains sulfur doping out-phase fenton catalyst.The mechanical property of sulfur doping out-phase fenton catalyst prepared by the present invention is also preferable, can be resistant to 30min ultrasound, and reclaims convenient, directly takes out all right to use water to clean, and can recycle；Sulfur doping out-phase fenton catalyst prepared by the present invention in neutral conditions, 60min can degrade more than 90% phenol.The present invention can obtain sulfur doping out-phase fenton catalyst.
Description
Technical field
The present invention relates to a kind of out-phase fenton catalyst and application.
Background technology
Fenton oxidation Guttae Phacosylini is catalyzed under the conditions of certain pH as homogeneous catalyst with homogeneous ferrous ion
H2O2, H2O2Produce hydroxyl radical free radical and carry out oxidative degradation organic pollution.However, homogeneous Fenton oxidation method, which has pH, is applicable model
Enclose that the narrow degradation efficiency i.e. under the conditions of the pH 3~4 is high, have iron cement generation in reaction, and catalyst lacking of can not recycling
Point, thus have developed it and widely use.In order to overcome the shortcoming of homogeneous Fenton reactions, iron is further developed on this basis
Base type Fenton catalyst.These catalyst exist with powder, and embryonic stem-like cells are needed to centrifuge or are separated by filtration after terminating,
In the presence of reclaiming, complicated, time-consuming, generally requires and haves the shortcomings that catalyst loss in 2h~5h, and removal process.Therefore, prepare
Returned with high catalytic activity, the immobilization film layer type Fenton catalyst being easily recycled for solving traditional type Fenton catalyst
The problem of recovering miscellaneous has great importance.
At present, differential arc oxidation law technology prepares ferriferous oxide film layer type Fenton catalyst, but its film on Q235 carbon steels
Layer bad mechanical property, ultrasound occurs that film layer comes off after 5 minutes；And although titanium alloy can obtain the film layer of good mechanical property,
But the correlative study of associated class fenton catalyst is less.
The content of the invention
It is long the invention aims to solve the existing homogeneous fenton catalyst reaction time, the applicable pH of Fenton's reaction system
Narrow range, catalyst can not reclaim and class fenton catalyst film layer poor mechanical property the problem of, and provide one kind in titanium alloy
Surface prepares method and the application of sulfur doping out-phase fenton catalyst.
A kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, is specifically realized by the following steps
's：
First, titanium alloy surface is pre-processed：
500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC are used successively
Sand paper carries out sanding and polishing to the surface of titanium alloy, is minute surface to the surface of titanium alloy, obtains the titanium alloy of surface-brightening；First
The titanium alloy of surface-brightening is cleaned 3 times~5 times using deionized water, then using titanium alloy of the absolute ethyl alcohol to surface-brightening
Cleaning 3 times~5 times, is finally dried up using hair-dryer, obtains pretreated titanium alloy；
2nd, electrolyte is prepared：
By NaSiO3·9H2O is added in deionized water, is stirred for NaSiO3·9H2O is completely dissolved, and adds time Asia
Sodium phosphate, is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are (15g~25g):1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.5g~1.5g):1L；
3rd, electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is put
In electrolyte, pretreated titanium alloy is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode
Connect, be used as negative electrode；Powered using constant-current pulse mao power source, be 0.06A/cm in current density2~0.5A/cm2, power supply
Frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 150s~300s,
Constant-current pulse mao power source is closed, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide
With sodium thiosulfate dissolving, then constant-current pulse mao power source is opened, then in current density be 0.06A/cm2~0.50A/
cm2, supply frequency 200Hz~2000Hz, the pH value of 25 DEG C~35 DEG C of electrolyte temperature and electrolyte react for 8~12 time
20min~40min, then pretreated titanium alloy is taken out, deionized water rinsing is reused 3 times~5 times, finally using blowing
Machine is dried up, and sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, is completed one kind and prepared sulfur doping in titanium alloy surface
The method of out-phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (3g~8g):1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~20g):1L.
Advantages of the present invention：
First, electrolyte system prepared by the present invention is stable, and alkaline system environmental pollution is small；Membrane aperture is widely distributed, both
There is projection there are many micro/nano level apertures again；
2nd, sulfur doping out-phase fenton catalyst prepared by the present invention can expand the application of fenton catalyst, Fenton
The application of reaction can be from highly acid to weakly acidic pH system；
3rd, the mechanical property of sulfur doping out-phase fenton catalyst prepared by the present invention is also preferable, can be resistant to the super of 30min
Sound, and reclaim convenient, directly takes out all right to use water to clean, and can recycle；
4th, the sulfur doping out-phase fenton catalyst for preparing of the present invention can degrade more than 90% phenol in 60min.
The present invention can obtain sulfur doping out-phase fenton catalyst.
Brief description of the drawings
Fig. 1 is the SEM figures of sulfur doping out-phase fenton catalyst prepared by embodiment one；
Fig. 2 is the SEM figures of sulfur doping out-phase fenton catalyst prepared by embodiment two；
Fig. 3 is the SEM figures of sulfur doping out-phase fenton catalyst prepared by embodiment three；
Fig. 4 is macro morphology of the sulfur doping out-phase fenton catalyst of the preparation of embodiment three after ultrasonic 30min；
Fig. 5 is the macro morphology that ceramic film class fenton catalyst prepared by contrast test passes through ultrasound 5min；
Fig. 6 is the degradation efficiency figure of the neutral phenolic waste water of degraded, and 1 is the degraded using titanium-based degradation of phenol waste water in Fig. 6
Efficiency curve, 2 be the degradation efficiency curve using iron-based degradation of phenol waste water, and 3 be that the sulfur doping prepared using embodiment three is different
The degradation efficiency curve of phase fenton catalyst；
It in the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4, Fig. 71 is real that Fig. 7, which is,
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4 of the preparation of example one is applied, 2 be embodiment
The efficiency curve of the two sulfur doping out-phase fenton catalysts prepared degradation of phenol under conditions of pH value is 4,3 be that embodiment three is made
The efficiency curve of standby sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4；
It in the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions, Fig. 81 is embodiment that Fig. 8, which is,
The efficiency curve of the three sulfur doping out-phase fenton catalysts degradation of phenol in neutral conditions prepared, 2 for second of circulation reality
The efficiency curve of the sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions of the preparation of example three is applied, 3 circulate for third time
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions for preparing of embodiment three.
Embodiment
Embodiment one：Present embodiment is a kind of to prepare sulfur doping out-phase fenton catalyst in titanium alloy surface
What method was specifically realized by the following steps：
First, titanium alloy surface is pre-processed：
500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC are used successively
Sand paper carries out sanding and polishing to the surface of titanium alloy, is minute surface to the surface of titanium alloy, obtains the titanium alloy of surface-brightening；First
The titanium alloy of surface-brightening is cleaned 3 times~5 times using deionized water, then using titanium alloy of the absolute ethyl alcohol to surface-brightening
Cleaning 3 times~5 times, is finally dried up using hair-dryer, obtains pretreated titanium alloy；
2nd, electrolyte is prepared：
By NaSiO3·9H2O is added in deionized water, is stirred for NaSiO3·9H2O is completely dissolved, and adds time Asia
Sodium phosphate, is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are (15g~25g):1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.5g~1.5g):1L；
3rd, electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is put
In electrolyte, pretreated titanium alloy is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode
Connect, be used as negative electrode；Powered using constant-current pulse mao power source, be 0.06A/cm in current density2~0.5A/cm2, power supply
Frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 150s~300s,
Constant-current pulse mao power source is closed, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide
With sodium thiosulfate dissolving, then constant-current pulse mao power source is opened, then in current density be 0.06A/cm2~0.50A/
cm2, supply frequency 200Hz~2000Hz, the pH value of 25 DEG C~35 DEG C of electrolyte temperature and electrolyte react for 8~12 time
20min~40min, then pretreated titanium alloy is taken out, deionized water rinsing is reused 3 times~5 times, finally using blowing
Machine is dried up, and sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, is completed one kind and prepared sulfur doping in titanium alloy surface
The method of out-phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (3g~8g):1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~20g):1L.
The advantage of present embodiment：
First, electrolyte system prepared by present embodiment is stable, and alkaline system environmental pollution is small；Membrane aperture distribution is wide
General, existing projection has many micro/nano level apertures again；
2nd, sulfur doping out-phase fenton catalyst prepared by present embodiment can expand the application of fenton catalyst,
The application of Fenton's reaction can be from highly acid to weakly acidic pH system；
3rd, the mechanical property of sulfur doping out-phase fenton catalyst prepared by present embodiment is also preferable, can be resistant to 30min
Ultrasound, and reclaim convenient, directly take out all right to use water to clean, can recycle；
4th, sulfur doping out-phase fenton catalyst prepared by present embodiment is under neutral system, and 60min can degrade 90%
Phenol above.
Present embodiment can obtain sulfur doping out-phase fenton catalyst.
Embodiment two：Present embodiment is with the difference of embodiment one：Described in step 2
NaSiO3·9H2O quality and the volume ratio of deionized water are (18g~23g):1L.Other steps and the phase of embodiment one
Together.
Embodiment three：One of present embodiment and embodiment one or two difference is：Institute in step 3
The quality for the sodium hypophosphite stated and the volume ratio of deionized water are (0.8g~1.2g):1L.Other steps and specific embodiment party
Formula one or two is identical.
Embodiment four：One of present embodiment and embodiment one to three difference is：Institute in step one
The titanium alloy stated is TC4.Other steps are identical with embodiment one to three.
Embodiment five：One of present embodiment and embodiment one to four difference is：Institute in step 3
The quality for the potassium ferricyanide stated and the volume ratio of electrolyte are (5g~8g):1L.Other steps and embodiment one to four
It is identical.
Embodiment six：One of present embodiment and embodiment one to five difference is：Institute in step 3
The quality for the sodium thiosulfate stated and the volume ratio of electrolyte are (1g~5g):1L.Other steps and embodiment one to
Five is identical.
Embodiment seven：One of present embodiment and embodiment one to six difference is：Institute in step 3
The quality for the sodium thiosulfate stated and the volume ratio of electrolyte are (5g~10g):1L.Other steps and embodiment one to
Six is identical.
Embodiment eight：One of present embodiment and embodiment one to seven difference is：Institute in step 3
The quality for the sodium thiosulfate stated and the volume ratio of electrolyte are (10g~15g):1L.Other steps and embodiment one
It is identical to seven.
Embodiment nine：One of present embodiment and embodiment one to eight difference is：Will in step 3
Electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is placed in electrolyte, in advance
Titanium alloy after processing is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode, is used as negative electrode；
Powered using constant-current pulse mao power source, be 0.06A/cm in current density2~0.1A/cm2, supply frequency 200Hz~
500Hz, 25 DEG C~30 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 150s~200s, close constant-current pulse
Mao power source, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide and sodium thiosulfate
Dissolving, then open constant-current pulse mao power source, then in current density be 0.06A/cm2~0.1A/cm2, supply frequency
200Hz~500Hz, 25 DEG C~30 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 20min~30min, then will
Pretreated titanium alloy takes out, and reuses deionized water rinsing 3 times~4 times, is finally dried up using hair-dryer, in titanium alloy table
Face obtains sulfur doping out-phase fenton catalyst, that is, completes a kind of side that sulfur doping out-phase fenton catalyst is prepared in titanium alloy surface
Method；Other steps are identical with embodiment one to eight.
Embodiment ten：One of present embodiment and embodiment one to nine difference is：Will in step 3
Electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is placed in electrolyte, in advance
Titanium alloy after processing is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode, is used as negative electrode；
Powered using constant-current pulse mao power source, be 0.2A/cm in current density2~0.3A/cm2, supply frequency 1000Hz~
2000Hz, 30 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 200s~300s, close constant-current pulse
Mao power source, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide and sodium thiosulfate
Dissolving, then open constant-current pulse mao power source, then in current density be 0.2A/cm2~0.3A/cm2, supply frequency 200Hz
~500Hz, 30 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 30min~40min, then will be located in advance
Titanium alloy after reason takes out, and reuses deionized water rinsing 4 times~5 times, is finally dried up, obtained in titanium alloy surface using hair-dryer
To sulfur doping out-phase fenton catalyst, that is, complete a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface；
Other steps are identical with embodiment one to nine.
Embodiment 11：Present embodiment is that sulfur doping out-phase fenton catalyst is used to handle phenolic waste water.
Embodiment 12：The difference of present embodiment and embodiment 11 is：Described sulfur doping
Out-phase fenton catalyst is completed according to the following steps for handling phenolic waste water：
Sulfur doping out-phase fenton catalyst is immersed in phenolic waste water, then low whipping speed is 100r/min~500r/
The hydrogen peroxide that concentration is 6mmol/L is added under min, then the pH value of phenolic waste water is adjusted to 4, then low whipping speed is 100r/
Stirring reaction 60min~80min, water after being handled under min~500r/min；Described sulfur doping out-phase fenton catalyst
Volume ratio (the 5cm of geometric area and phenolic waste water2~10cm2):50mL；The concentration of phenol is 20mg/ in described phenolic waste water
L~50mg/L；The geometric area of described sulfur doping out-phase fenton catalyst and volume ratio of the concentration for 6mmol/L hydrogen peroxide
For (5cm2~10cm2):50mL。
Other are identical with embodiment 11.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, specifically by following
What step was completed：
First, titanium alloy surface is pre-processed：
500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC are used successively
Sand paper carries out sanding and polishing to the surface of titanium alloy, is minute surface to the surface of titanium alloy, obtains the titanium alloy of surface-brightening；First
The titanium alloy of surface-brightening is cleaned 4 times using deionized water, 4 then are cleaned to the titanium alloy of surface-brightening using absolute ethyl alcohol
It is secondary, finally dried up using hair-dryer, obtain pretreated titanium alloy；
Titanium alloy described in step one is TC4；
2nd, electrolyte is prepared：
By NaSiO3·9H2O is added in deionized water, is stirred for NaSiO3·9H2O is completely dissolved, and adds time Asia
Sodium phosphate, is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are 20g:1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are 1.0g:1L；
3rd, electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is put
In electrolyte, pretreated titanium alloy is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode
Connect, be used as negative electrode；Powered using constant-current pulse mao power source, be 0.06A/cm in current density2, supply frequency 500Hz,
The pH value of 30 DEG C of electrolyte temperature and electrolyte is 10 times reaction 150s, constant-current pulse mao power source is closed, to electrolyte
The middle addition potassium ferricyanide and sodium thiosulfate, is stirred for the potassium ferricyanide and sodium thiosulfate dissolving, then to open constant-current pulse micro-
Arc aoxidize power supply, then current density be 0.06A/cm2, supply frequency 200Hz, the pH value of 30 DEG C of electrolyte temperature and electrolyte
20min are reacted for 10 times, then pretreated titanium alloy is taken out, deionized water rinsing are reused 4 times, finally using hair-dryer
Drying, sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, completing one kind, in titanium alloy surface to prepare sulfur doping different
The method of phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are 5g:1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are 5g:1L.
Embodiment two：A kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, specifically by following
What step was completed：
First, titanium alloy surface is pre-processed：
500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC are used successively
Sand paper carries out sanding and polishing to the surface of titanium alloy, is minute surface to the surface of titanium alloy, obtains the titanium alloy of surface-brightening；First
The titanium alloy of surface-brightening is cleaned 4 times using deionized water, 4 then are cleaned to the titanium alloy of surface-brightening using absolute ethyl alcohol
It is secondary, finally dried up using hair-dryer, obtain pretreated titanium alloy；
Titanium alloy described in step one is TC4；
2nd, electrolyte is prepared：
By NaSiO3·9H2O is added in deionized water, is stirred for NaSiO3·9H2O is completely dissolved, and adds time Asia
Sodium phosphate, is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are 20g:1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are 1.0g:1L；
3rd, electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is put
In electrolyte, pretreated titanium alloy is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode
Connect, be used as negative electrode；Powered using constant-current pulse mao power source, be 0.06A/cm in current density2, supply frequency 500Hz,
The pH value of 30 DEG C of electrolyte temperature and electrolyte is 10 times reaction 150s, constant-current pulse mao power source is closed, to electrolyte
The middle addition potassium ferricyanide and sodium thiosulfate, is stirred for the potassium ferricyanide and sodium thiosulfate dissolving, then to open constant-current pulse micro-
Arc aoxidize power supply, then current density be 0.06A/cm2, supply frequency 200Hz, the pH value of 30 DEG C of electrolyte temperature and electrolyte
20min are reacted for 10 times, then pretreated titanium alloy is taken out, deionized water rinsing are reused 4 times, finally using hair-dryer
Drying, sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, completing one kind, in titanium alloy surface to prepare sulfur doping different
The method of phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are 5g:1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are 10g:1L.
Embodiment three：A kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, specifically by following
What step was completed：
First, titanium alloy surface is pre-processed：
500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC are used successively
Sand paper carries out sanding and polishing to the surface of titanium alloy, is minute surface to the surface of titanium alloy, obtains the titanium alloy of surface-brightening；First
The titanium alloy of surface-brightening is cleaned 4 times using deionized water, 4 then are cleaned to the titanium alloy of surface-brightening using absolute ethyl alcohol
It is secondary, finally dried up using hair-dryer, obtain pretreated titanium alloy；
Titanium alloy described in step one is TC4；
2nd, electrolyte is prepared：
By NaSiO3·9H2O is added in deionized water, is stirred for NaSiO3·9H2O is completely dissolved, and adds time Asia
Sodium phosphate, is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are 20g:1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are 1.0g:1L；
3rd, electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is put
In electrolyte, pretreated titanium alloy is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode
Connect, be used as negative electrode；Powered using constant-current pulse mao power source, be 0.06A/cm in current density2, supply frequency 500Hz,
The pH value of 30 DEG C of electrolyte temperature and electrolyte is 10 times reaction 150s, constant-current pulse mao power source is closed, to electrolyte
The middle addition potassium ferricyanide and sodium thiosulfate, is stirred for the potassium ferricyanide and sodium thiosulfate dissolving, then to open constant-current pulse micro-
Arc aoxidize power supply, then current density be 0.06A/cm2, supply frequency 200Hz, the pH value of 30 DEG C of electrolyte temperature and electrolyte
20min are reacted for 10 times, then pretreated titanium alloy is taken out, deionized water rinsing are reused 4 times, finally using hair-dryer
Drying, sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, completing one kind, in titanium alloy surface to prepare sulfur doping different
The method of phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are 5g:1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are 15g:1L.
Contrast test：One kind prepares ceramic film class Fenton on Q235 carbon steels surface using plasma electrolytic oxidation method and urged
The method of agent, is completed according to the following steps：
First, Q235 carbon steels pre-treatment：Successively using the table of 500# sand paper, 1500# sand paper and 2500# sand paper to Q235 carbon steels
The surface that face carries out being polishing to Q235 carbon steels is minute surface；Using deionized water rinsing Q235 carbon steels surface 4 times, anhydrous second is reused
Alcohol rinses Q235 carbon steels surface 4 times, is finally dried up using hair-dryer, obtains the Q235 carbon steels of light；
2nd, the bright Q235 carbon steels obtained in step one are placed in the electrolyte in stainless steel electrolytic groove, are used as sun
Pole；Stainless steel electrolytic groove is connected with power cathode, is used as negative electrode；
3rd, powered using the pulse power, be 12A/cm in current density2, supply frequency 2000Hz, 30 DEG C of electrolyte temperature
With electrolyte ph be 14.0 under conditions of carry out plasma electrolytic oxidation reaction 20min, made pottery on Q235 carbon steels surface
Porcelain film layer class fenton catalyst, that is, complete one kind and prepare ceramic film on Q235 carbon steels surface using plasma electrolytic oxidation method
The method of class fenton catalyst；
Electrolyte described in step 3 is made up of sodium metasilicate, sodium hypophosphite and water；Sodium metasilicate in described electrolyte
Concentration be 25g/L；The concentration of sodium hypophosphite is 1g/L in described electrolyte.
Fig. 1 is the SEM figures of sulfur doping out-phase fenton catalyst prepared by embodiment one；
From fig. 1, it can be seen that there are some projections and hole in the surface of sulfur doping out-phase fenton catalyst prepared by embodiment one, and
Also hole is distributed in projection.
Fig. 2 is the SEM figures of sulfur doping out-phase fenton catalyst prepared by embodiment two；
As can be seen from Figure 2, there are more projection and hole in the surface of sulfur doping out-phase fenton catalyst prepared by embodiment two,
And also hole is distributed in projection.
Fig. 3 is the SEM figures of sulfur doping out-phase fenton catalyst prepared by embodiment three；
As can be seen from Figure 3, there are substantial amounts of projection and hole in the surface of sulfur doping out-phase fenton catalyst prepared by embodiment three,
And in projection in addition to hole, also many particles.
Sulfur doping out-phase fenton catalyst prepared by embodiment three ultrasound in ultrasonic power is 60W distilled water
30min, the macro morphology of sulfur doping out-phase fenton catalyst prepared by embodiment three after ultrasonic 30min is as shown in Figure 4；
Fig. 4 is macro morphology of the sulfur doping out-phase fenton catalyst of the preparation of embodiment three after ultrasonic 30min；
As can be seen from Figure 4, the sulfur doping out-phase fenton catalyst that prepared by embodiment three still compares on surface after ultrasonic 30min
More complete, film layer engineering properties is stable.
Ceramic film class fenton catalyst prepared by the contrast test ultrasound in ultrasonic power is 60W distilled water
5min, the grand smooth pattern of ceramic film class fenton catalyst prepared by contrast test after ultrasonic 5min is as shown in Figure 5；
Fig. 5 is the macro morphology that ceramic film class fenton catalyst prepared by contrast test passes through ultrasound 5min；
As can be seen from Figure 5, the ceramic film class fenton catalyst that prepared by contrast test has gone out on surface after ultrasonic 5min
Show film layer to come off.
Fig. 4 and Fig. 5 is the digital photograph shot using digital camera.
The Degrading experiment one of phenol：
By 6cm2Titanium alloy TC 4 be added in 50mL neutral phenolic waste water, then low whipping speed be 300r/min under
The hydrogen peroxide that 34 μ L concentration are 30% is added, then low whipping speed is stirring reaction 0min~75min under 300r/min, is obtained everywhere
Water after reason；The concentration of phenol is 35mg/L in described neutral phenolic waste water, and degraded situation is as shown in Fig. 61；
By 6cm2Q235 alloys be added in the neutral phenolic waste waters of 50mL, then low whipping speed is to add under 300r/min
34 μ L concentration are 30% hydrogen peroxide, then low whipping speed is stirring reaction 0min~75min under 300r/min, is obtained after processing
Water；The concentration of phenol is 35mg/L in described neutral phenolic waste water, and degraded situation is as shown in Fig. 62；
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment three be immersed in the neutral phenolic waste waters of 50mL, then
Low whipping speed is that the hydrogen peroxide that 34 μ L concentration are 30% is added under 300r/min, then low whipping speed is to stir under 300r/min
React 0min~75min, water after being handled；The concentration of phenol is 35mg/L in described neutral phenolic waste water, situation of degrading
As shown in Fig. 63；
Fig. 6 is the degradation efficiency figure of degradation of phenol waste water, and 1 is the degradation efficiency using titanium-based degradation of phenol waste water in Fig. 6
Curve, 2 be the degradation efficiency curve using iron-based degradation of phenol waste water, and 3 be the sulfur doping out-phase sweet smell prepared using embodiment three
The degradation efficiency curve of catalyst；
As can be seen from Figure 6, in neutral conditions, 60min's sulfur doping out-phase fenton catalyst that prepared by embodiment three can degrade
More than 90% phenol, and the degraded of titanium alloy and iron Pyrogentisinic Acid has almost no change.
The Degrading experiment two of phenol：
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment one be immersed in 50mL phenolic waste waters, then stirring
It is to add the hydrogen peroxide that 34 μ L concentration are 30% under 300r/min to mix speed, and it is 0.01mol/L dilute sulfuric acids by benzene to reuse concentration
The pH value of phenol waste water is adjusted to 4.0, then low whipping speed is stirring reaction 0min~75min under 300r/min, is obtained after processing
Water；The concentration of phenol is 35mg/L in described phenolic waste water, and degraded situation is as shown in Fig. 71；
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment two be immersed in 50mL phenolic waste waters, then stirring
It is to add the hydrogen peroxide that 34 μ L concentration are 30% under 300r/min to mix speed, and it is 0.01mol/L dilute sulfuric acids by benzene to reuse concentration
The pH value of phenol waste water is adjusted to 4.0, then low whipping speed is stirring reaction 0min~75min under 300r/min, is obtained after processing
Water；The concentration of phenol is 35mg/L in described phenolic waste water, and degraded situation is as shown in Fig. 72；
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment three be immersed in 50mL phenolic waste waters, then stirring
It is to add the hydrogen peroxide that 34 μ L concentration are 30% under 300r/min to mix speed, and it is 0.01mol/L dilute sulfuric acids by benzene to reuse concentration
The pH value of phenol waste water is adjusted to 4.0, then low whipping speed is stirring reaction 0min~75min under 300r/min, is obtained after processing
Water；The concentration of phenol is 35mg/L in described phenolic waste water, and degraded situation is as shown in Fig. 73；
It in the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4, Fig. 71 is real that Fig. 7, which is,
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4 of the preparation of example one is applied, 2 be embodiment
The efficiency curve of the two sulfur doping out-phase fenton catalysts prepared degradation of phenol under conditions of pH value is 4,3 be that embodiment three is made
The efficiency curve of standby sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4；
As can be seen from Figure 7, with the increase of sulphur source content, the degradation rate of phenol is accelerated.
The Degrading experiment three of phenol：By 6cm2Embodiment three prepare sulfur doping out-phase fenton catalyst be immersed in 50mL
In neutral phenolic waste water, then low whipping speed is to add the hydrogen peroxide that 34 μ L concentration are 30% under 300r/min, then in stirring
Speed is stirring reaction 0min~80min, water after being handled under 300r/min；Phenol in described neutral phenolic waste water
Concentration is 35mg/L, and degraded situation is as shown in Fig. 81；
Cycle performance experiment one：The system of embodiment three after the degradation of phenol 75min that will be obtained in the Degrading experiment three of phenol
Standby sulfur doping out-phase fenton catalyst is taken out, and reuses distilled water and cleans 5 times, then is dried in vacuo 10h in the case where temperature is 60 DEG C,
Obtain sulfur doping out-phase fenton catalyst prepared by the embodiment three of second of circulation；It is prepared by the embodiment three of second of circulation
Sulfur doping out-phase fenton catalyst be immersed in the neutral phenolic waste waters of 50mL, then low whipping speed is to add under 300r/min
34 μ L concentration are 30% hydrogen peroxide, then low whipping speed is stirring reaction 0min~90min under 300r/min, is obtained after processing
Water；The concentration of phenol is 35mg/L in described neutral phenolic waste water, and degraded situation is as shown in Fig. 82；
Cycle performance experiment two：Cycle performance is tested to second of circulation after the degradation of phenol 90min obtained in one
Sulfur doping out-phase fenton catalyst prepared by embodiment three is taken out, and reuses distilled water and cleans 5 times, then in the case where temperature is 60 DEG C very
Sky dries 10h, obtains the sulfur doping out-phase fenton catalyst for the preparation of embodiment three that third time is circulated；By the reality of third time circulation
The sulfur doping out-phase fenton catalyst for applying the preparation of example three is immersed in the neutral phenolic waste waters of 50mL, then low whipping speed is
Added under 300r/min 34 μ L concentration be 30% hydrogen peroxide, then low whipping speed be 300r/min under stirring reaction 0min~
90min, water after being handled；In described neutral phenolic waste water the concentration of phenol be 35mg/L, degraded situation such as Fig. 8 in 3
It is shown；
It in the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions, Fig. 81 is embodiment that Fig. 8, which is,
The efficiency curve of the three sulfur doping out-phase fenton catalysts degradation of phenol in neutral conditions prepared, 2 for second of circulation reality
The efficiency curve of the sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions of the preparation of example three is applied, 3 circulate for third time
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions for preparing of embodiment three.
As it can be observed in the picture that embodiment three prepare sulfur doping out-phase fenton catalyst circulate three times, in neutral conditions still
There is degradation property.
Claims (10)
1. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, it is characterised in that one kind is in titanium alloy table
What the method that face prepares sulfur doping out-phase fenton catalyst was specifically realized by the following steps：
First, titanium alloy surface is pre-processed：
500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC sand paper are used successively
Sanding and polishing is carried out to the surface of titanium alloy, is minute surface to the surface of titanium alloy, obtains the titanium alloy of surface-brightening；First by
Deionized water is cleaned 3 times~5 times to the titanium alloy of surface-brightening, and then the titanium alloy of surface-brightening is cleaned using absolute ethyl alcohol
3 times~5 times, finally dried up using hair-dryer, obtain pretreated titanium alloy；
2nd, electrolyte is prepared：
By NaSiO3·9H2O is added in deionized water, is stirred for NaSiO3·9H2O is completely dissolved, and adds ortho phosphorous acid
Sodium, is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are (15g~25g):1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.5g~1.5g):1L；
3rd, electrolyte is added in stainless steel electrolytic groove, then the pretreated titanium alloy obtained in step one is placed in electricity
Solve in liquid, pretreated titanium alloy is connected with positive source, is used as anode；Stainless steel electrolytic groove is connected with power cathode,
It is used as negative electrode；Powered using constant-current pulse mao power source, be 0.06A/cm in current density2~0.5A/cm2, supply frequency
200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value are 8~12 times reaction 150s~300s, are closed
Constant-current pulse mao power source, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide and sulphur
Sodium thiosulfate dissolves, then opens constant-current pulse mao power source, then in current density is 0.06A/cm2~0.50A/cm2, electricity
Source frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value be 8~12 time react 20min~
40min, then pretreated titanium alloy is taken out, reuse deionized water rinsing 3 times~5 times, finally dried up using hair-dryer,
Sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, completes one kind and prepares sulfur doping out-phase Fenton in titanium alloy surface
The method of catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (3g~8g):1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~20g):1L.
2. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
Levy and be NaSiO described in step 23·9H2O quality and the volume ratio of deionized water are (18g~23g):1L.
3. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
The volume ratio for levying the quality for being the sodium hypophosphite described in step 3 and deionized water is (0.8g~1.2g):1L.
4. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
Levy and be that the titanium alloy described in step one is TC4.
5. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
The volume ratio for levying the quality for being the potassium ferricyanide described in step 3 and electrolyte is (5g~8g):1L.
6. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
The volume ratio for levying the quality for being the sodium thiosulfate described in step 3 and electrolyte is (1g~5g):1L.
7. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
The volume ratio for levying the quality for being the sodium thiosulfate described in step 3 and electrolyte is (5g~10g):1L.
8. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, it is special
The volume ratio for levying the quality for being the sodium thiosulfate described in step 3 and electrolyte is (10g~15g):1L.
9. prepared according to a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface as claimed in claim 1
Sulfur doping out-phase fenton catalyst application, it is characterised in that sulfur doping out-phase fenton catalyst be used for handle phenolic waste water.
10. the application of sulfur doping out-phase fenton catalyst according to claim 9, it is characterised in that described sulfur doping is different
Phase fenton catalyst is completed according to the following steps for handling phenolic waste water：
Sulfur doping out-phase fenton catalyst is immersed in phenolic waste water, then low whipping speed is under 100r/min~500r/min
Add the hydrogen peroxide that concentration is 6mmol/L, then the pH value of phenolic waste water adjusted to 4, then low whipping speed be 100r/min~
Stirring reaction 60min~80min, water after being handled under 500r/min；The geometry of described sulfur doping out-phase fenton catalyst
Volume ratio (the 5cm of area and phenolic waste water2~10cm2):50mL；In described phenolic waste water the concentration of phenol be 20mg/L~
50mg/L；The volume ratio for the hydrogen peroxide that the geometric area of described sulfur doping out-phase fenton catalyst is 6mmol/L with concentration is
(5cm2~10cm2):50mL。
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