CN104909435B - A kind of glycine doped polyaniline modified electrode and its preparation method and application - Google Patents
A kind of glycine doped polyaniline modified electrode and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of glycine doped polyaniline modified electrode and its preparation method and application, this electrode includes electrode base material, and the reactive end surface modification of electrode base material has polyaniline, doped with glycine on polyaniline.Its preparation method includes setting up three-electrode system, the modification of glycine doped polyaniline.The glycine doped polyaniline modified electrode of the present invention has the advantages that high adsorption, high reproducibility and high stability, can be used in processing containing hexavalent chromium wastewater, simultaneously by the method for polarity switching, is capable of to the advanced treating containing hexavalent chromium wastewater.The application process of the present invention is a kind of green technology processing containing hexavalent chromium wastewater, and, with electronics directly as reducing agent, it is harmless to have a cleaning, the features such as environmental friendliness, simultaneously because it need not add other extra reducing agents, greatly reduces the yield of mud for it.
Description
Technical field
The present invention relates to water-treatment technology field, more particularly, to a kind of glycine doped polyaniline modified electrode and its system
Preparation Method and application.
Background technology
Chromium in water body is mainly derived from the industries such as plating, coating material production, textile industry, process hides, wood preservation.Chromium mainly with
Presented in Cr VI and trivalent chromium, wherein Cr VI has strong oxidizing property, high toxicity, easy animal migration and carcinogenecity, its poison
Property be chromic 500 times.In view of the hazardness of pollution of chromium, EPA is classified as chromium as priority pollutant (Priority
Pollutants), and specify that the concentration of total chromium in drinking water should be less than 0.1mg/L, World Health Organization (WHO) also specifies chromic
It is 0.005mg/L that highest allows concentration of emission, and the chromic limit value of domestic water quality standard for drinking water is 0.05mg/L.Therefore, such as
It is the final steps processing hexavalent chromium wastewater that highly toxic Cr VI is fast and effeciently converted to hypotoxic trivalent chromium by what.
The method containing hexavalent chromium wastewater that processed by this process at present mainly includes chemical reduction method and electrochemical reduction
Method two big class.Wherein chemical reduction method is mainly by adding reducing substanceses, for example ferrous iron, sulphite and sulfide
Deng, but such method can produce substantial amounts of toxic sludge, easily causes its secondary pollution.And electrochemical reduction rule is to pass through
Cr VI is converted to trivalent chromium by cathode electronics transmission, and it need not add reproducibility chemical substance, and mud yield is very little,
Can be rated as the green technology of hexavalent chromium-treatments.
But this technology still suffers from deficiency many as follows at present：1) compared to the Cr VI of high concentration, the six of low concentration
Valency chromium is more difficult to be efficiently removed；2) electrode specific surface area is less, reduces the transmission efficiency of electronics；3) Cr VI is with anion
Form exists, and electric field force makes it be difficult to obtain electronics near cathode surface.Above deficiency also limit the extensive application of this technology.
Content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided one kind has high adsorption, height
The glycine doped polyaniline modified electrode of reproducibility and high stability, additionally provides this glycine doped polyaniline and repaiies
The preparation method and application of decorations electrode.
For solving above-mentioned technical problem, the invention provides a kind of glycine doped polyaniline modified electrode, including electricity
Pole base material, the reactive end surface modification of electrode base material has polyaniline, doped with glycine on polyaniline.
Further, former electrodes base material has netted or cavernous structure.
As the same technology design of the present invention, present invention also offers aforesaid glycine doped polyaniline modifies electricity
The preparation method of pole, comprises the following steps：
S1, aniline, polyvinyl alcohol, sulphuric acid, glycine are hybridly prepared into aqueous solution, as electrolyte solution；With electrode
As working electrode, as to electrode, silver/silver chloride electrode, as reference electrode, sets up three-electrode system to platinized platinum to base material；
Carry out a volt-ampere scan round, when the effective body of the unit at anode peak in S2, the three-electrode system set up in step sl
Long-pending electric current density reaches and stops scanning during saturation value, completes the preparation of glycine doped polyaniline modified electrode.
In step S1 of preparation method of the present invention, electrode base material is preferably reticulated vitreous carbon, and the hole density of electrode base material is
30～100PPI (average number of pores in inches length).Electrode base material, using front, is carried out ultrasonic successively using second alcohol and water
Cleaning, the wherein volume fraction of ethanol are 80%～90%, and cleaning temperature is 20 DEG C～50 DEG C.
Further, in abovementioned steps S1, electrolyte solution is also included before use except oxygen pre-treatment step：Toward aforementioned water
It is passed through the nitrogen that flow is 20mL/min～50mL/min in solution to carry out except oxygen treatments applied 20min～40min.
Further, in abovementioned steps S1, in electrolyte solution, the concentration of aniline is 5g/L～18g/L, polyvinyl alcohol dense
Spend for 0.5g/L～3g/L, the volume fraction of sulphuric acid is 10～30%, the concentration of glycine is 4g/L～12g/L.
Further, in abovementioned steps S2, the current potential of volt-ampere scan round is -0.3V～1.0V, and scanning speed is 20mV/
S～60mV/s；The current potential at anode peak is 0.1V～0.3V；Saturation value is 3000A/m3～6000A/m3；The number of repetition of step S2
For 2 times～4 times.Current potential employed in volt-ampere scan round process is with respect to the current potential of silver/silver chloride electrode.
As the same technology design of the present invention, present invention also offers a kind of aforesaid glycine doped polyaniline is repaiied
Adorn glycine doped polyaniline modified electrode the answering in processing containing hexavalent chromium wastewater that electrode or aforementioned preparation process are obtained
With.
Further, aforementioned applications comprise the following steps：To contain hexavalent chromium wastewater be added to poly- including glycine doping
In the electrolysis system of aniline modified electrode and inert electrode, on glycine doped polyaniline modified electrode and inert electrode
Apply square pulse electric current and carry out Electrochemical adsorption reduction reaction, complete to the process containing hexavalent chromium wastewater.
Further, the polarity switching cycle of aforementioned square pulse electric current is 1s～300s, and size of current is 0.1～10A.
Further, aforementioned pH value containing hexavalent chromium wastewater is adjusted according to following correlation：PH=-lg [Cr (VI)/
(mol/L)], wherein Cr (VI) is chromic concentration in waste water.
In the application of the present invention, electrolysis system adopts DC source, and the inert electrode in electrolysis system is preferably Ti electrode.
Compared with prior art, it is an advantage of the current invention that：
(1) the invention provides a kind of glycine doped polyaniline modified electrode, adopt poly- doped with glycine
Aniline is modified in the surface at electrode reaction end, and wherein glycine has specific chemical characterization of adsorption, energy to hexavalent chromium
Enough Cr VIs by low concentration adsorb in electrode surface, realize its enrichment method；Simultaneously the polyaniline of electrode surface have excellent
Electrochemical reduction characteristic, be capable of the quick transmission of electronics.Therefore, the present invention passes through in electrode face finish doped with ammonia
The polyaniline of guanidine-acetic acid, makes electrode have the advantages that high adsorption, high reproducibility and high stability it is achieved that to containing Cr VI
The advanced treating of waste water.
(2) the invention provides a kind of preparation method of glycine doped polyaniline modified electrode, make full use of amino
Acetic acid and the feature of polyaniline, successfully glycine are entrained on polyaniline using volt-ampere periodic scan method (CV), are prepared for
A kind of glycine doped polyaniline modified electrode.Wherein electrolyte solution adopts aniline, polyvinyl alcohol, sulphuric acid, glycine to mix
Conjunction is configured to aqueous solution, and polyvinyl alcohol therein significantly improves the stability of glycine doped polyaniline modified electrode；And
Using electrode base material as working electrode, as to electrode, silver/silver chloride electrode, as reference electrode, sets up three electrode body to platinized platinum
System, has the advantage of regulation and control easy to operate.The present invention makes the aniline in solution real under specific potential using volt-ampere periodic scan method
Existing autocatalytic polymerization, its nitrogen carries positive charge, carries the glycine of negative charge simultaneously and carry positive charge nitrogen in solution
In conjunction with and be doped in the main polymer chain being grown into, compared to additive method, there is the advantages such as motility height, easy-regulating, make
The electrode stability preparing is higher.
(3) the invention provides a kind of glycine doped polyaniline modified electrode contains answering in hexavalent chromium wastewater in process
With, because hexavalent chromium is negatively charged, in the presence of Traditional DC electric field, leading to it to be difficult to the modified electrode as negative electrode
Surface aggregation, on the contrary to anode surface aggregation, this feature has become electrochemical reduction technology and has removed chromic restricted step
Suddenly.And the present invention is modified using a kind of glycine doped polyaniline with high adsorption, high reproducibility and high stability
Electrode, simultaneously by the method for polarity switching, realizes it to the advanced treating containing hexavalent chromium wastewater.The present invention passes through the amino that adulterates
Acetic acid achieves the efficient absorption characteristic of electrode pair hexavalent chromium, by the absorption of the Cr VI of low concentration in electrode surface so as to
Enrichment method；Realize the quick transmission of electronics using the polyaniline of electrode surface simultaneously.Additionally, by square pulse electric current, real
The switching of existing direction of an electric field is so that hexavalent chromium can be to modified electrode surface migration in the presence of electric field force, further
Strengthen it and modify electrode surface gathering, thus realizing the advanced treating containing hexavalent chromium wastewater.The present invention makes full use of square arteries and veins
Rush the feature of electric current, constantly switch the polarity of modified electrode.When modified electrode is for anode, hexavalent chromium gathers to its surface
Collection, and it is modified the glycine absorption of electrode；Then when modified electrode switches to negative electrode, in the presence of polyaniline, sexavalence
Chromium ion quickly obtains electronics in modification electrode surface, realizes its efficiently reduction removal.Electrochemical reduction of the present invention
Mode is a kind of green technology processing containing hexavalent chromium wastewater, and it has harmless, the environment of cleaning with electronics directly as reducing agent
Friendly the features such as；Simultaneously because it need not add other extra reducing agents, greatly reduce the yield of mud.
Brief description
Purpose, technical scheme and advantage for making the embodiment of the present invention are clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the preparation method flow chart of glycine doped polyaniline modified electrode in the embodiment of the present invention 1.
Fig. 2 is the volt-ampere scan round figure preparing glycine doped polyaniline modified electrode in the embodiment of the present invention 1.
Fig. 3 is the electron microscope of the glycine doped polyaniline modified electrode of preparation in the embodiment of the present invention 1.
Fig. 4 be the embodiment of the present invention 1 in preparation glycine doped polyaniline modified electrode energy spectrum diagram.
Fig. 5 is that in the embodiment of the present invention 2, glycine doped polyaniline modified electrode is used for processing containing hexavalent chromium wastewater
Square pulse current diagram.
Fig. 6 is for glycine doped polyaniline modified electrode in the embodiment of the present invention 2 after processing containing hexavalent chromium wastewater
Energy spectrum diagram.
Specific embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Material employed in following examples and instrument are commercially available.
Embodiment
A kind of glycine doped polyaniline modified electrode of present invention, including electrode base material, wherein electrode base material is anti-
End surfaces are answered to be modified with polyaniline, doped with glycine on polyaniline.In the present embodiment, electrode base material be hole density 30～
The reticulated vitreous carbon of 100PPI.
A kind of preparation method of above-mentioned glycine doped polyaniline modified electrode, comprises the following steps：
S1, take electrode base material as working electrode, platinized platinum as to electrode, silver/silver chloride electrode as reference electrode, with
Aniline, polyvinyl alcohol, sulphuric acid, the aqueous solution of glycine are electrolyte solution, set up three-electrode system；
S2, step S1 set up three-electrode system in carry out a volt-ampere scan round, when the unit effective volume at anode peak
Electric current density reaches and stops scanning during saturation value, is cleaned by ultrasonic working electrode, obtains glycine doped polyaniline modified electrode.
It is preferred that electrode base material includes reticulated vitreous carbon in the preparation method of the present embodiment.Electrode base material use front, according to
Secondary be cleaned by ultrasonic using second alcohol and water, wherein the volume fraction of ethanol be 80～90%, cleaning temperature be 20 DEG C～
50℃.
It is preferred that in aqueous solution, the concentration of aniline is 5g/L～18g/L, polyvinyl alcohol in the preparation method of the present embodiment
Concentration be 0.5g/L～3g/L, the volume fraction of sulphuric acid is 10～30%, and the concentration of glycine is 4g/L～12g/L.Its
In, aqueous solution, using front, also includes except oxygen pretreatment：It is passed through the nitrogen that flow is 20mL/min～50mL/min toward in aqueous solution
Gas is carried out except oxygen treatments applied 20min～40min.
It is preferred that the current potential of volt-ampere scan round is -0.3V～1.0V in the preparation method of the present embodiment, scanning speed
For 20mV/s～60mV/s；The current potential at anode peak is 0.1V～0.3V；Unit effective volume electric current density saturation value is 3000A/
m3～6000A/m3.Current potential employed in volt-ampere scan round process is with respect to the current potential of silver/silver chloride electrode.Step S2
Number of repetition be 2 times～4 times.
The glycine that a kind of above-mentioned glycine doped polyaniline modified electrode or above-mentioned preparation method are obtained is mixed
Application in processing containing hexavalent chromium wastewater for the miscellaneous polyaniline modified electrode.
It is preferred that comprising the following steps in the application of the present embodiment：Hexavalent chromium wastewater will be contained be added to including glycine
In the electrolysis system of doped polyaniline modified electrode and inert electrode, in glycine doped polyaniline modified electrode and inertia electricity
The extremely upper square pulse electric current that applies carries out Electrochemical adsorption reduction reaction, completes to the process containing hexavalent chromium wastewater.
It is preferred that the polarity switching cycle of square pulse electric current is 1s～300s in the application of the present embodiment, size of current
For 0.1～10A.
It is preferred that pH value containing hexavalent chromium wastewater is adjusted according to following correlation in the application of the present embodiment：PH=-
Lg [Cr (VI)/(mol/L)], wherein Cr (VI) are chromic concentration in waste water.
It is preferred that electrolysis system includes DC source in the application of the present embodiment, the inert electrode in electrolysis system includes
Ti electrode.
Embodiment 1：
A kind of glycine doped polyaniline modified electrode of present invention, including electrode base material, wherein electrode base material is anti-
End surfaces are answered to be modified with polyaniline, doped with glycine on polyaniline.
In the present embodiment, electrode base material is reticulated vitreous carbon.
A kind of preparation method of the glycine doped polyaniline modified electrode in above-mentioned the present embodiment, as shown in figure 1, bag
Include following steps：
(1) pre-treatment of electrode base material：Selection hole density is 30ppi, and a height of 15mm × 15mm of length and width × 50mm's is netted
Vitreous carbon, as electrode base material, is immersed in the ethanol that volume fraction is 85%, after being cleaned by ultrasonic 15min at 40 DEG C,
Deionized water is cleaned by ultrasonic 3 times.
(2) prepare electrolyte solution：Aniline, polyvinyl alcohol, sulphuric acid, glycine are hybridly prepared into aqueous solution, as electricity
Solution matter liquid, the wherein concentration of aniline are 9g/L, and the concentration of polyethylene is alcohol 2g/L, the volume fraction 20% of sulphuric acid, glycine
Concentration be 8g/L.By the electrolyte solution preparing in 25 DEG C of ultrasonic dissolution 10min, then it is passed through flow for 30mL/min nitrogen
30min, removes oxygen therein, completes the preparation of electrolyte solution.
(3) set up three-electrode system：Three-electrode system, wherein work are built with Shanghai occasion China CHI760E electrochemical workstation
Making electrode is the electrode base material after pre-treatment in step (1), and its effective dimensions is 15mm × 15mm × 40mm；To electrode it is
The platinized platinum of 10mm × 10mm；Reference electrode is silver/silver chloride electrode.The electricity that will prepare in three-electrode system inserting step (2)
In electrolyte solution, the mixing speed keeping electrolyte solution is 300rpm, and temperature is 25 DEG C, and is passed through the nitrogen that flow is 30mL/min
Gas.
(4) modification of glycine doped polyaniline：Carry out volt-ampere circulation to sweep in the three-electrode system that step (3) builds
Retouch, wherein temperature is 25 DEG C, the scanning potential range of volt-ampere circulation is -0.1 to arrive 0.8V, and scanning speed is 40mV/s, with sweeping
Retouch the increase of the number of turns, at 0.2V on volt-ampere cyclic curve, the unit effective volume electric current density at anode peak is also gradually increased, when it
Reach saturation value 5000A/m3When then stop scan, the current potential employed in volt-ampere scan round process is with respect to silver/chlorination
Then modified electrode deionized water is cleaned by ultrasonic 5min by the current potential of silver electrode.Above modification step repeats 3 times, that is, obtain
Glycine doped polyaniline modified electrode.
Fig. 2 is the volt-ampere scan round figure preparing glycine doped polyaniline modified electrode, as can be seen from Figure 2 with
The increase of scanning times, at 0.2V on curve, anodic peak current density is stepped up, show glycine doped polyaniline simultaneously
Progressively layering is attached to the surface of electrode base material so that modified electrode surface area increases.
Fig. 3 is the electron-microscope scanning of the glycine doped polyaniline modified electrode being prepared using the method for embodiment 1
Figure, as can be seen from Figure 3 electrode base material has loose structure, and its surface is covered by glycine doped polyaniline.
Fig. 4 be embodiment 1 in preparation glycine doped polyaniline modified electrode energy spectrum diagram, from energy spectrum analysiss table
Bright modified electrode is 8.63% nitrogen containing mass fraction and mass fraction is 0.68% element sulphur, shows glycine success
Doped polyaniline.
Embodiment 2
A kind of glycine doped polyaniline modified electrode of embodiment 1 is in processing containing Cr VI (Cr (VI)) waste water
Application, comprises the steps：
(1) water quality conditioning：In waste water, the concentration of Cr (VI) is 52mg/L (10-3Mol/L), according to pH=-lg [Cr (VI)/
(mol/L)] calculate, by waste water pH regulator to 3.0, and import in the reactor of 500mL.
(2) polarity switching strengthening Electrochemical adsorption reduction：One piece of glycine doped polyaniline that embodiment 1 is obtained is repaiied
The titanium pole plate (as the inert electrode of the present embodiment) that decorations electrode is 500mm × 1500mm with one piece of area is placed in parallel in
In reactor.The waste water after water quality conditioning equipped with step (1) in the reactor.Glycine doping polyphenyl by embodiment 1
Amine-modified electrode is connected with the time relay (time relay is purchased from Shanghai Zhuo one, model ZYT18), and the time relay passes through again
Wire is connected with the negative pole of DC source (DC source is purchased from Beijing Pu Yuan, model DP1116A)；Titanium electrode and time continue
Electrical equipment is connected, and the time relay is connected with the anode of DC source by wire again, and setting size of current is 0.1A, time relay
The square pulse electric current (as shown in Figure 5) of device polarization switching cycle T=4s, realizes glycine doped polyaniline and modifies electricity
The continuous switching of pole polarity, carries out Electrochemical adsorption reduction reaction, and the response time is 60min, completes to containing hexavalent chromium wastewater
Process.With the content of Cr (VI) as measurement index, the glycine doped polyaniline modified electrode investigating embodiment 1 is to Cr (VI)
Removal efficiency, investigate the results are shown in Table 1.
Comparative example 1
A kind of preparation method of the modified electrode of comparative example, in addition in electrolyte solution without polyvinyl alcohol, other
Part is same as Example 1.
The modified electrode of comparative example 1 is processed and contains Cr VI (Cr (VI)) waste water, its processing method is same as Example 2.
With the content of Cr (VI) as measurement index, investigate the removal efficiency to Cr (VI) for the modified electrode of comparative example 1, investigate result and be listed in
In table 1.
Comparative example 2
A kind of preparation method of the modified electrode of comparative example, in addition in electrolyte solution without glycine, other
Part is same as Example 1.
The modified electrode of comparative example 2 is processed and contains Cr VI (Cr (VI)) waste water, its processing method is same as Example 2.
With the content of Cr (VI) as measurement index, investigate the removal efficiency to Cr (VI) for the modified electrode of comparative example 2, investigate result and be listed in
In table 1.
Use continuous for the modified electrode of embodiment 1, comparative example 1 and comparative example 2 50 times respectively simultaneously, process and contain Cr VI
Waste water, with the removal efficiency of Cr (VI) as measurement index, investigates the stability of glycine doped polyaniline modified electrode, stable
Property investigate the results are shown in Table 1.
Table 1：Cr (VI) removal efficiency (%) comparing result
Understand from the estimation of stability result of table 1：The guanidine-acetic acid doped polyaniline modified electrode of embodiment 1 is through 50 times
After use, the removal to Cr (VI) still has very high removal efficiency (98.32%), and its treatment effeciency only have dropped
1.46%.
After the electrode of comparative example 1 recycles through 50 times, Cr (VI) removal efficiency be have dropped with 13.26%, and embodiment 1
Glycine doped polyaniline modified electrode only have dropped 1.46%.Result shows, polyvinyl alcohol is conducive to strengthening electrode
Stability and ruggedness.
After the electrode of comparative example 2 recycles through 50 times, it is 81.82% to Cr (VI) removal efficiency, and the ammonia of embodiment 1
Guanidine-acetic acid doped polyaniline modified electrode is 98.32%.Result shows, glycine has stronger absorption and makees to Cr (VI)
With, the substantial amounts of hexavalent chromium of its surface adsorption, its mass fraction is 13.84% (see Fig. 6), therefore passes through the glycine that adulterates
The removal efficiency of Cr (VI) can be improved.
Comparative example 3
A kind of embodiment 1 glycine doped polyaniline modified electrode processing containing in Cr VI (Cr (VI)) waste water
Application, its application process is with the difference of embodiment 2：Do not carry out polarity switching electric current, specially adopt polarity not
The cathode current becoming, is according to said method processed and contains hexavalent chromium wastewater, continuously use 50 times, referred to for measurement with the removal efficiency of Cr (VI)
Mark, the stability of inspecting electrode, its study on the stability result is as shown in table 2.
Table 2：Cr (VI) removal efficiency (%) comparing result
Understand from the estimation of stability result of table 2：After recycling through 50 times in comparative example 3, effect is removed to Cr (VI)
Rate is 78.57%, and adopts the processing method of embodiment 2, is 98.32% to Cr (VI) removal efficiency.Result shows, polarity is cut
Transducing enough utilizes the electrostatic force of electric field, promotes negatively charged Cr (VI) to glycine doped polyaniline modified electrode table
Face migrates, and therefore can improve the removal efficiency of Cr (VI) by polarity switching.
Embodiment 3
One piece of glycine doped polyaniline modified electrode that embodiment 1 is obtained is used for processing the sexavalence containing variable concentrations
Chrome waste water.Except chromic concentration and corresponding pH different with process time in addition to, its process step is same as Example 2.
With the removal efficiency of Cr (VI) and stability as measurement index, investigate modified electrode and its method to variable concentrations containing sexavalence
The suitability of chrome waste water and through 50 times recycle after modified electrode stability, investigate the results are shown in Table 3.
Table 3：Different Cr (VI) removal efficiency and stability analyses
As known from Table 3, under different initial Cr (VI) concentration of 26～520mg/L, the glycine doping polyphenyl of embodiment 1
The removal efficiency removal efficiency of amine-modified electrode pair heavy metal Cr (VI) is very high, has reached more than 99.74%.Simultaneously through 50
After secondary reuse, its removal efficiency fall is less than 1.96%, has very high stability.
Embodiment 4
One piece of glycine doped polyaniline modified electrode that embodiment 1 is obtained is used for investigating opposed polarity switching cycle
Square pulse electric current for the impact containing hexavalent chromium wastewater treatment effect, and modified electrode through 50 times recycle after
The impact of stability.In addition to the polarity switching cycle of square pulse electric current is different with process time, its process step and enforcement
Example 2 is identical.The results are shown in Table 4 for investigation.
Table 4：Opposed polarity switching cycle and electrode cycle access times are to Cr (VI) removal efficiency (%)
As shown in Table 4, within the polarity switching cycle of 1 selected～300s, chromic removal efficiency be 99.62～
99.85%.After 50 times recycle, chromic removal efficiency is between 98.3～98.64%.Test result indicate that pole
In 1～300s, this electrode still has very high treatment effeciency and stability to property switching cycle.
The above, be only presently preferred embodiments of the present invention, and not the present invention is made with any pro forma restriction.Though
So the present invention is disclosed as above with preferred embodiment, but is not limited to the present invention.Any it is familiar with those skilled in the art
Member, in the case of the spirit without departing from the present invention and technical scheme, can be utilized in the methods and techniques of the disclosure above
Hold and technical solution of the present invention is made with many possible variations and modification, or the Equivalent embodiments being revised as equivalent variations.Therefore,
Every content without departing from technical solution of the present invention, the technical spirit of the foundation present invention is to made for any of the above embodiments any simple
Modification, equivalent, equivalence changes and modification, all still fall within the range of technical solution of the present invention protection.
Claims (10)
1. a kind of glycine doped polyaniline modified electrode it is characterised in that include electrode base material, described electrode base material anti-
End surfaces are answered to be modified with polyaniline, doped with glycine on described polyaniline.
2. glycine doped polyaniline modified electrode according to claim 1 is it is characterised in that described electrode base material has
There is netted or cavernous structure.
3. a kind of preparation method of glycine doped polyaniline modified electrode as claimed in claim 1 or 2, walks including following
Suddenly：
S1, aniline, polyvinyl alcohol, sulphuric acid, glycine are hybridly prepared into aqueous solution, as electrolyte solution；With electrode base material
As working electrode, as to electrode, silver/silver chloride electrode, as reference electrode, sets up three-electrode system to platinized platinum；
Carry out a volt-ampere scan round, when the unit effective volume electricity at anode peak in S2, the three-electrode system set up in step sl
Current density reaches and stops scanning during saturation value, completes the preparation of glycine doped polyaniline modified electrode.
4. preparation method according to claim 3 is it is characterised in that in described step S1, described electrolyte solution is using
Front also include except oxygen pre-treatment step：It is passed through the nitrogen that flow is 20mL/min～50mL/min to carry out toward in described aqueous solution
Except oxygen treatments applied 20min～40min.
5. the preparation method according to claim 3 or 4 is it is characterised in that in the described electrolyte solution of described step S1, institute
The concentration stating aniline is 5g/L～18g/L, and the concentration of described polyvinyl alcohol is 0.5g/L～3g/L, the volume fraction of described sulphuric acid
For 10～30%, the concentration of described glycine is 4g/L～12g/L.
6. the preparation method according to claim 3 or 4 is it is characterised in that in described step S2, described volt-ampere scan round
Current potential be -0.3V～1.0V, scanning speed be 20mV/s～60mV/s；The current potential at described anode peak is 0.1V～0.3V；Institute
Stating saturation value is 3000A/m3～6000A/m3；The number of repetition of described step S2 is 2 times～4 times.
7. a kind of glycine doped polyaniline modified electrode as any one of claim 1 and 2 or such as claim 3
The glycine doped polyaniline modified electrode that preparation method any one of～6 is obtained is in processing containing hexavalent chromium wastewater
Application.
8. application according to claim 7 is it is characterised in that described application process comprises the following steps：Cr VI will be contained
Waste water is added in the electrolysis system including described glycine doped polyaniline modified electrode and inert electrode, in described amino
Square pulse electric current is applied on acetic acid doped polyaniline modified electrode and inert electrode and carries out Electrochemical adsorption reduction reaction, complete
To the process containing hexavalent chromium wastewater.
9. according to claim 8 application it is characterised in that described square pulse electric current the polarity switching cycle be 1s～
300s, size of current is 0.1～10A.
10. application according to claim 8 or claim 9 is it is characterised in that described pH value containing hexavalent chromium wastewater is according to following association
Formula is adjusted：PH=-lg [Cr (VI)/(mol/L)], wherein Cr (VI) are chromic molar concentration in waste water, and unit is
mol/L.
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