CN108163932A - A kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode - Google Patents
A kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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Abstract
The present invention is a kind of preparation method of the lead dioxide electrode of the three-dimensional structure of doped metal ion.This method will use potentiostatic method, by the use of the oxygen bubbles of precipitation as dynamic template, by the control to current potential and sedimentation time, by the metal oxide and PbO of the elements such as manganese, cerium, lanthanum, bismuth, iron, cobalt2Matrix surface is equably co-deposited to, the PbO of the three-dimensional macroporous structure of doping different metal ions is made2Electrode.With three-dimensional macroporous structure M/PbO obtained2Electrode is anode (M represents different metal ions), carries out Electrocatalysis Degradation to alizarin red, removal rate is up to 88%~95.1%.With the pure PbO of three-dimensional structure2Electrode is compared, and this new electrode material that the present invention obtains has better effect in organic matter degradation processing.
Description
Technical field
The present invention relates to a kind of preparation methods of the lead dioxide electrode of the three-dimensional macroporous structure of doped metal ion.
Background technology
With science and technology and industrialized rapid development, the limitation that conventional anode material is shown is more and more, example
Cost such as platinum electrode is too high, and the corrosion resistance of graphite base electrode is poor etc., it is impossible to it is high to meet low consumption in modern industry again
Output, low input high repayment, green pollution-free demand, therefore find it is a kind of it is cheap, corrosion resistance is good, urges
The strong and environmentally friendly anode material of change ability is extremely urgent.
Lead dioxide electrode, because it is with overpotential for oxygen evolution is higher, corrosion resistance is preferable, stability is preferable, oxidability
Compared with the advantages that strong, electric conductivity is good and cheap, in electrochemical field such as lead-acid accumulator, electrochemistry formated and organic contamination
Object wastewater treatment etc. has important application, also more and more interested to researchers.The titanium-based titanium dioxide of early application
Lead does not have middle layer between titanium-based and brown lead oxide, which results in internal stress between electrode is larger, easy to fall off, stability is low, greatly
The big service life for shortening electrode, affects application of the electrode in electro-catalysis field.To overcome the above disadvantages, researchers
Tin antimony middle layer is increased between matrix and titanium dioxide lead layer.But the catalytic performance of this electrode is still relatively low, in order into
One step improves the catalytic performance of lead dioxide electrode, and researchers in the active coating of electrode by adulterating Bi3+、Co2+、Ce3 +、La3+、Fe3+Deng some special ions, using the electric conductivity and catalytic activity of metal ion itself, improve the electricity of electrode with this
Catalytic activity enhances the degradation capability to organic pollution.But it is two by lead dioxide electrode made from the above method
Dimensional plane structure, the effective electro catalytic activity area of electrode is still smaller, limited to the castering action of electrocatalysis characteristic.It is and three-dimensional big
Pore structure has larger transmission channel, is conducive to contaminant molecule and enters in duct, effectively expands the electro-catalysis area of electrode,
Have become a completely new direction of lead dioxide electrode research at present.
This seminar had previously prepared the lead dioxide electrode of three-dimensional structure in anode using oxygen bubbles template
(Preparation and Electrocatalytic Performance of Three-Dimensional Porous
Structure PbO2Electrodes Using Oxygen Bubble as Dynamic Templates.Yingwu Yao,
Xin Chen,Naichuan Yu,Haishu Dong,Haoren Wang.ISSN:0013-4651).The electrode, which has, continuously to be passed through
Logical three-dimensional macroporous structure, greatly improves electro-catalysis area, so as to improve the electro catalytic activity of electrode and catalytic efficiency.
This subsequent seminar passes through compound ZrO2Nano particle using bubble template composite electrodeposition technique, has obtained three-dimensional structure
PbO2-ZrO2Combination electrode (Preparation and Characterization of a Porous Structure
PbO2-ZrO2Nanocomposite Electrode and Its Application in Electrocatalytic
Degradation ofCrystal Violet.Yingwu Yao,Chunjiao Huang,Xin Chen,Feng Wei,
HuailiangFeng.ISSN:0013-4651).Pass through the PbO in three-dimensional structure2Compound ZrO in electrode2Nano particle, with this
To improve the stability of three-dimensional structure electrode.But due to ZrO2For inertia nano particle, the electrocatalysis characteristic of electrode is promoted
It is limited.
Invention content
It is an object of the invention to be directed to the two-dimension plane structure PbO of doped metal ion2Effective electricity is urged existing for electrode
Change active area is small, catalytic activity is low and the pure PbO of three-dimensional structure2The problems such as electrode electro catalytic activity is low, provide one kind and mix
The preparation method of the lead dioxide electrode of the three-dimensional structure of miscellaneous metal ion.This method will use potentiostatic method, utilize precipitation
Oxygen bubbles is as dynamic template, by the control to current potential and sedimentation time, by the metal of the elements such as manganese, cerium, lanthanum, bismuth, iron, cobalt
Oxide and PbO2Matrix surface is equably co-deposited to, the PbO of the three-dimensional structure of doping different metal ions is made2Electrode.This
Invent obtained this new electrode material has better effect in organic matter degradation processing.
The technical scheme is that：
A kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode, includes the following steps：
(1) using pretreated Ti plates as matrix, intermediate layer solution is coated in titanium plate surface, then at 100~120 DEG C
Lower drying 10-20min；The thermal oxide 20-120min at 200-500 DEG C again；Then the step of repetitive coatings-drying-calcining
Totally 8~10 times, final coated weight is that Ti coated weights every square centimeter are 5~10g, obtains Ti/SnO2-Sb2O5Electrode；
The middle layer is by SnCl2·2H2O、SbCl3, n-butanol and concentrated hydrochloric acid mix, mass ratio is
SnCl2·2H2O：SbCl3：N-butanol：Concentrated hydrochloric acid=(9-1):(1-9):(20-50):(5-10)；
(2) Ti/SnO for obtaining upper step2-Sb2O5Electrode is for the three-dimensional macroporous structure of doping metal ion
PbO2Layer electrodes：Using stereotype as cathode, Ti/SnO2-Sb2O5Electrode carries out electro-deposition for anode, wherein, plating solution composition is tool
Have a metal salt of identical anion and the solution of lead salt, a concentration of 0.1-0.5mol/L of lead salt, metal salt concentrations for 1mmol/L~
Between 5mmol/L, pH controls are 1~3, technological parameter：Controlling potential is 4.5V~6V, and sedimentation time is 1800s- at room temperature
3600s finally obtains the PbO of the three-dimensional macroporous structure of doping different metal ions2Electrode；
The pretreatment is to carry out polishing grinding after Ti matrixes are cut, and then uses the NaOH heat alkali liquids of 10-20%
Alkali cleaning, then the oxalic acid aqueous solution pickling with 10-20% are carried out, after washing, is carved at room temperature with 1%~3% oxalic acid aqueous solution
Erosion 1-2 days or so, is finally rinsed well with deionized water.
The metal salt be specially manganese, cerium, lanthanum, bismuth, iron, cobalt salt it is one or more.Preferably bismuth or manganese both
Metal salt.
The anion is specially nitrate ion.
The concentration of NaF in the step (2) is preferably 1g/L.
The PbO of the three-dimensional macroporous structure of the doped metal ion2The application of electrode, for industrial wastewater to be catalytically decomposed
In organic dyestuff.
The present invention substantive distinguishing features be：
In order to further improve the electro catalytic activity of three-dimensional structure lead dioxide electrode, the present invention is by adulterating Bi, Mn, Ce
Metal ions are waited, using the electro catalytic activity of metal ion itself, realize that improving three-dimensional macroporous structure lead dioxide electrode electricity urges
Change the purpose of activity.And the titanium dioxide of the three-dimensional macroporous structures of metal cation components such as doping Bi, Mn, Ce is successfully prepared
Lead electrode material, so far, still not about three-D pore structure brown lead oxide of the preparation containing metal ions such as Bi, Mn, Ce
The relevant report of electrode.
Beneficial effects of the present invention are：
The present invention is to provide a kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode.The party
Method use potentiostatic method, be carried out at the same time the electrodeposition process of oxygen evolution reaction and brown lead oxide, by the use of precipitation oxygen bubbles as
The PbO of the three-dimensional structure of doping different metal ions is made in dynamic template2Electrode, the two dimension electricity with Traditional dopant metal ion
Pole is compared, which has the macroporous structure continuously penetrated through, is conducive to contaminant molecule and enters in duct, so as to improve electrode
Electro catalytic activity and catalytic efficiency.With the pure PbO of three-dimensional structure2Electrode is compared, which has due to being doped with metal ion
There are the electric conductivity and catalytic activity of metal ion so that the catalytic performance of electrode improves.
With the present invention using three-dimensional macroporous structure M/PbO obtained2Electrode is anode (M represents different metal ions),
Stereotype, using two electrode systems, industrial wastewater is simulated by target contaminant of alizarin red as cathode, DC power supply power supply, right
Alizarin red organic dyestuff carries out Electrocatalysis Degradation.By attached drawing 8 it is found that three-dimensional macroporous structure M/PbO2Removal of the electrode to alizarin red
Rate is 88%~95.1%.And the pure lead dioxide electrode of three-dimensional structure is only 71.3% to the removal rate of alizarin red, thus may be used
After knowing doped metal ion, the PbO of three-dimensional structure2The catalytic performance of electrode all increases, and the degree only improved is slightly not
Together.By attached drawing 9 it is found that the doping Bi of two-dimensional structure3+PbO2Electrode is 72.6% to the removal rate of alizarin red, with three-dimensional structure
Bi/PbO2Electrode is compared, and the catalytic efficiency of two-dimensional structure is relatively low.In conclusion the three-dimensional structure titanium dioxide of doped metal ion
The electro catalytic activity of lead electrode significantly improves.
Description of the drawings
Fig. 1 is the Mn/PbO of three-dimensional macroporous structure made from embodiment 12The local SEM figures of electrode.
Fig. 2 is the Ce/PbO of three-dimensional macroporous structure made from embodiment 22The local SEM figures of electrode.
Fig. 3 is the La/PbO of three-dimensional macroporous structure made from embodiment 32The local SEM figures of electrode.
Fig. 4 is the Bi/PbO of three-dimensional macroporous structure made from embodiment 42The local SEM figures of electrode.
Fig. 5 is the Bi/PbO of three-dimensional macroporous structure made from embodiment 52The local SEM figures of electrode.
Fig. 6 is the Fe/PbO of three-dimensional macroporous structure made from embodiment 62The local SEM figures of electrode.
Fig. 7 is the Co/PbO of three-dimensional macroporous structure made from embodiment 72The local SEM figures of electrode.
Fig. 8 is the pure PbO of three-dimensional structure2Electrode and three-dimensional structure M/PbO2The removal rate of electrode degrading alizarin red becomes at any time
Change figure.
Fig. 9 is two-dimensional structure Bi/PbO2Electrode and three-dimensional structure Bi/PbO2The removal rate of electrode degrading alizarin red is at any time
Variation diagram.
Specific embodiment
It illustrates below in conjunction with the accompanying drawings and the present invention is described in more detail：
Embodiment 1
1. the Mn/PbO of three-dimensional macroporous structure2The preparation of electrode material
(1) pretreatment of Ti matrixes.Ti plates (purity is TA2 ranks) are cut to 2cm*5cm first, are polished polishing
Processing then carries out alkali cleaning, then the oxalic acid aqueous solution pickling with 10-20% with the NaOH heat alkali liquids of 10-20%, after washing, uses
1%~3% oxalic acid aqueous solution etches 1-2 days or so at room temperature, is finally rinsed well with deionized water.The purpose of pretreatment
It is the greasy dirt and oxidation film removed on Ti plates.
(2) SnO is coated2-Sb2O5Middle layer.Using pretreated Ti plates as matrix, titanium plate surface is applied with middle layer
It covers uniformly, is then put into baking oven and dries 10min at 110 DEG C；Muffle furnace is put into after taking out to be calcined, it is hot at 300 DEG C
20min is aoxidized, then the step of repetitive coatings-drying-calcining totally 10 times, muffle furnace is stepped up, when temperature reaches
It is sintered 2h at 500 DEG C to terminate, obtains the Ti/SnO that unit area coated weight is 5g2-Sb2O5Electrode；Coat SnO2-Sb2O5It is intermediate
The purpose of layer is to improve the binding force of Ti matrixes and lead dioxide plating coat.
The middle layer is by SnCl of the quality for 9g2·2H2O、1gSbCl3, 20g n-butanols and 10g concentrated hydrochloric acids mixing and
Into.(above-mentioned drug is the pure rank of analysis, 38%) mass fraction of concentrated hydrochloric acid is
(3) in SnO2-Sb2O5Middle layer powers on the Mn/PbO of deposition three-dimensional structure2Coating.It is 0.2mol/ in plating solution composition
L Pb(NO3)2, 5mmol/L Mn (NO3)2, use HNO3PH is adjusted to 2.0~3.0 by (mass fraction 65%-68%), solvent
For in the solution of water, using stereotype as cathode, Ti/SnO2-Sb2O5Electro-deposition is carried out for anode, technological parameter is set：Constant potential
5.0V 1800s is deposited at room temperature.The Mn/PbO of three-dimensional structure is made2Coating material.
By SEM figures local in attached drawing 1 it is found that three-dimensional macroporous structure Mn/PbO produced by the present invention2Coating material has
There are significant penetrated macropore structure, the Mn/PbO with two-dimensional structure2Electrode is compared, and porous structure causes the active sites of electro-catalysis
Point increases, and the area of electro-catalysis is effectively expanded, so as to improve electrocatalysis characteristic.Additionally due to metal oxide itself is led
Electrical and catalytic activity so that the electro catalytic activity for adulterating the lead dioxide electrode of the three-dimensional structure of manganese ion improves.
Embodiment 2
Other steps are 0.2mol/LPb (NO the difference lies in plating solution composition with embodiment 13)2, 3mmol/L Ce
(NO3)3, technological parameter when setting electro-deposition is constant potential 4.5V, deposits 3000s at room temperature.Three-dimensional macroporous structure is made
Ce/PbO2Electrode.Attached drawing 2 represents the Ce/PbO of three-dimensional macroporous structure obtained2Electrode part SEM schemes.
Embodiment 3
Other steps are 0.2mol/LPb (NO the difference lies in plating solution composition with embodiment 13)2, 1mmol/L La
(NO3)3, PH 2.0, technological parameter when setting electro-deposition is constant potential 5V, deposits 3000s at room temperature.Three-dimensional structure is made
La/PbO2Electrode.Attached drawing 3 represents that the La/PbO of three-dimensional structure is made2The local SEM figures of electrode.
Embodiment 4
Other steps are 0.2mol/L Pb (NO the difference lies in plating solution composition with embodiment 13)2, 5mmol/L Bi
(NO3)3·5H2Between O, PH are 1.0~1.5, technological parameter during electro-deposition is set for constant potential 4.5V~5V, room temperature
Lower deposition 1800s.The Bi/PbO of three-dimensional macroporous structure is made2Electrode.Attached drawing 4 represents that the Bi/PbO of three-dimensional structure is made2Electrode
Local SEM figures.
Example 5
Other steps are with embodiment 4, and the difference lies in it is constant potential 5V to set technological parameter during electro-deposition, room temperature
Lower deposition 6000s.The Bi/PbO prepared on this condition2Electrode.As shown in figure 5, schemed by SEM it can be seen that making under this condition
Standby electrode has not had porous structure, and pore structure disappears, and final electrode surface is by brown lead oxide crystal grain and micro metal
Oxide is completely covered.This is because during overlong time, coating is blocked up to collapse three-dimensional macroporous structure.
Embodiment 6
Other steps are 0.2mol/LPb (NO the difference lies in plating solution composition with embodiment 13)2, 1mmol/LFe
(NO3)3, PH 2, technological parameter when setting electro-deposition is constant potential 5V, deposits 3000s at room temperature.Three-dimensional macroporous structure is made
Fe/PbO2Electrode.Attached drawing 6 represents that the Fe/PbO of three-dimensional structure is made2The local SEM figures of electrode.
Embodiment 7
Other steps are 0.2mol/LPb (NO the difference lies in plating solution composition with embodiment 13)2, 1~3mmol/L Co
(NO3)2, a concentration of 2mmol/L Co (NO of best addition3)2, PH 2, it is constant potential to set technological parameter during electro-deposition
6V deposits 3000s~3600s at room temperature.The Co/PbO of three-dimensional macroporous structure is made2Electrode.Attached drawing 7 represents that three-dimensional structure is made
Co/PbO2The local SEM figures of electrode.
2 three-dimensional structure M/PbO2The electrocatalysis characteristic research of electrode
With the present invention using three-dimensional macroporous structure M/PbO obtained2Electrode is anode (M represents different metal ions),
Stereotype, using two electrode systems, industrial wastewater is simulated by target contaminant of alizarin red as cathode, DC power supply power supply, right
Alizarin red organic dyestuff carries out Electrocatalysis Degradation, as experimental group；It is tied using the pure lead dioxide electrode and two dimension of three-dimensional structure
The Bi/PbO of structure2For electrode respectively as anode, remaining condition is constant, and Electrocatalysis Degradation is carried out to alizarin red organic dyestuff, as
Control group.The volume of alizarin red aqueous solution is 100ml, a concentration of 50mg/L, current density 30mA/cm2.It is three-dimensional after being electrolysed 90min
Macroporous structure M/PbO2Electrode is to the removal rate of alizarin red 88%~95.1%.And the pure lead dioxide electrode pair of three-dimensional structure
The removal rate of alizarin red is only 71.3%, after understanding doped metal ion by attached drawing 8, the PbO of three-dimensional structure2The catalytic of electrode
It can all increase, the degree only improved is slightly different.The doping Bi of two-dimensional structure3+PbO2Removal of the electrode to alizarin red
Rate is 72.6%, with three-dimensional structure Bi/PbO2Electrode is compared, and the catalytic efficiency of two-dimensional structure is relatively low, this is primarily due to three-dimensional
The electrode of structure has larger electro catalytic activity area.Its comparing result figure is shown in attached drawing 9.
By embodiment 1,2,3,4,6,7 as can be seen that can be made under the conditions of appropriate current potential and reasonable time
For the PbO for the three-dimensional macroporous structure for going out doped metal ion2Electrode, the PbO with the doped metal ion of two-dimensional structure2Electrode phase
Than the electrode of three-dimensional structure has porous structure, and catalytic activity improves；With the pure PbO of three-dimensional macroporous structure2Electrode is compared,
Due to the electric conductivity and catalytic activity of metal ion itself, pass through the PbO in three-dimensional macroporous structure2In electrode doping metals from
Son is modified it, further improves the PbO of three-dimensional macroporous structure2The catalytic performance of electrode can preferably be applied to have
Machine pollutant process field.Example 5 illustrates overlong time for preparing the PbO of the three-dimensional macroporous structure of doped metal ion2
Electrode is unfavorable, and during main cause overlong time, coating is blocked up also to collapse three-dimensional macroporous structure；In addition time mistake
Short situation be known situation, PbO2Coating is also unformed, can not form three-dimensional structure.
Therefore, the present invention provides the three-dimensional macroporous structure PbO of doped metal ion2The preparation method of electrode, this method
The PbO of the three-dimensional structure of the doped metal ion of preparation2Electrode, this new electrode material have the macropore knot continuously penetrated through
Structure, simultaneously as being doped with metal ion, the electric conductivity and catalytic activity of electrode all significantly improve.Gold is adulterated with two-dimensional structure
Belong to the PbO of ion2Electrode and the pure PbO of three-dimensional macroporous structure2Electrode is compared, and this new electrode material produced by the present invention is urged
Change activity and catalytic efficiency is obviously improved, and preparation process is simple, it is of low cost, in practical applications with wide development before
Scape.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. a kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode, it is characterized in that this method include with
Lower step：
（1）Using pretreated Ti plates as matrix, intermediate layer solution is coated in titanium plate surface, is then dried at 100 ~ 120 DEG C
Dry 10-20min；The thermal oxide 20-120min at 200-500 DEG C again；Then the step of repetitive coatings-drying-calcining totally 8 ~
10 times, final coated weight is that Ti coated weights every square centimeter are 5 ~ 10g, obtains Ti/SnO2-Sb2O5Electrode；
The middle layer is by SnCl2•2H2O、SbCl3, n-butanol and concentrated hydrochloric acid mix, mass ratio SnCl2•2H2O：
SbCl3：N-butanol：Concentrated hydrochloric acid=(9-1):(1-9):(20-50):(5-10)；
（2）The Ti/SnO that upper step is obtained2-Sb2O5Electrode is used for the PbO of the three-dimensional macroporous structure of doping metal ion2
Layer electrodes：Using stereotype as cathode, Ti/SnO2-Sb2O5Electrode carries out electro-deposition for anode, wherein, plating solution composition is with phase
With the metal salt of anion and the solution of lead salt, a concentration of 0.1-0.5mol/L of lead salt, metal salt concentrations for 1mmol/L ~
Between 5mmol/L, pH controls are 1 ~ 3, technological parameter：Controlling potential is 4.5V ~ 6V, and sedimentation time is 1800s- at room temperature
3600s finally obtains the PbO of the three-dimensional macroporous structure of doping different metal ions2Electrode；
The pretreatment is to carry out polishing grinding after Ti matrixes are cut, and then carries out alkali with the NaOH heat alkali liquids of 10-20%
It washes, then the oxalic acid aqueous solution pickling with 10-20%, after washing, a 1-2 days left sides is etched at room temperature with 1% ~ 3% oxalic acid aqueous solution
The right side is finally rinsed well with deionized water；
The metal salt be specially manganese, cerium, lanthanum, bismuth, iron, cobalt salt it is one or more；
The anion is specially nitrate ion.
2. the PbO of the three-dimensional macroporous structure of doped metal ion as described in claim 12The preparation method of electrode, it is characterized in that
The step（2）In NaF a concentration of 1 g/L.
3. the PbO of the three-dimensional macroporous structure of doped metal ion as described in claim 12The preparation method of electrode, it is characterized in that
The metal salt is bismuth or the metal salt of manganese.
4. the PbO of the three-dimensional macroporous structure of doped metal ion as described in claim 12The preparation method of electrode, it is characterized in that
For the organic dyestuff in industrial wastewater to be catalytically decomposed.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892288A (en) * | 2018-06-27 | 2018-11-27 | 中国石油天然气集团有限公司 | A kind of oil field waste liquid electro-catalysis high-efficient decolorizing method and device |
| CN111785536A (en) * | 2020-08-11 | 2020-10-16 | 苏州柯诺思高新材料有限公司 | Preparation method of asymmetric capacitor nano lead dioxide based composite electrode |
| CN113697908A (en) * | 2021-09-13 | 2021-11-26 | 东莞理工学院 | Preparation method of electrode for electrocatalytic degradation of printing and dyeing wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108892288A (en) * | 2018-06-27 | 2018-11-27 | 中国石油天然气集团有限公司 | A kind of oil field waste liquid electro-catalysis high-efficient decolorizing method and device |
| CN108892288B (en) * | 2018-06-27 | 2022-02-01 | 中国石油天然气集团有限公司 | Electrocatalysis high-efficiency decolorization method and device for oil field waste liquid |
| CN111785536A (en) * | 2020-08-11 | 2020-10-16 | 苏州柯诺思高新材料有限公司 | Preparation method of asymmetric capacitor nano lead dioxide based composite electrode |
| CN113697908A (en) * | 2021-09-13 | 2021-11-26 | 东莞理工学院 | Preparation method of electrode for electrocatalytic degradation of printing and dyeing wastewater |
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