CN112174266A - Method for preparing bionic electropolymerization layer at constant potential in one step and application of bionic electropolymerization layer in degradation of printing and dyeing wastewater - Google Patents
Method for preparing bionic electropolymerization layer at constant potential in one step and application of bionic electropolymerization layer in degradation of printing and dyeing wastewater Download PDFInfo
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- 238000004043 dyeing Methods 0.000 title claims abstract description 24
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- 238000000034 method Methods 0.000 title claims abstract description 19
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- 238000006731 degradation reaction Methods 0.000 title abstract description 5
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- 239000000178 monomer Substances 0.000 claims abstract description 13
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- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
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- 238000001035 drying Methods 0.000 claims description 16
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 claims description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 10
- ODFFPRGJZRXNHZ-UHFFFAOYSA-N 5-fluoroindole Chemical compound FC1=CC=C2NC=CC2=C1 ODFFPRGJZRXNHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- LOJNBPNACKZWAI-UHFFFAOYSA-N 3-nitro-1h-pyrrole Chemical compound [O-][N+](=O)C=1C=CNC=1 LOJNBPNACKZWAI-UHFFFAOYSA-N 0.000 claims description 7
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 235000012207 sodium gluconate Nutrition 0.000 claims description 6
- 239000000176 sodium gluconate Substances 0.000 claims description 6
- 229940005574 sodium gluconate Drugs 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- DXIHILNWDOYYCH-UHDJGPCESA-M sodium;(e)-3-phenylprop-2-enoate Chemical compound [Na+].[O-]C(=O)\C=C\C1=CC=CC=C1 DXIHILNWDOYYCH-UHDJGPCESA-M 0.000 claims description 6
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 claims description 5
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 5
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 claims description 5
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 claims description 5
- 235000007746 carvacrol Nutrition 0.000 claims description 5
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 5
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229960004025 sodium salicylate Drugs 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 3
- 229930016911 cinnamic acid Natural products 0.000 claims description 3
- 235000013985 cinnamic acid Nutrition 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- -1 β -aminopyrrole Chemical compound 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 32
- 239000007787 solid Substances 0.000 abstract description 22
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 239000013047 polymeric layer Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 12
- 229940097275 indigo Drugs 0.000 description 12
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 12
- 244000137852 Petrea volubilis Species 0.000 description 10
- 238000004042 decolorization Methods 0.000 description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 10
- 229910010271 silicon carbide Inorganic materials 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
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- 238000007334 copolymerization reaction Methods 0.000 description 4
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- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910001250 2024 aluminium alloy Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920001103 Poly(o-methoxyaniline) Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229920001577 copolymer Chemical group 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Electrochemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for preparing a bionic electropolymerization layer by one step at constant potential and application of the bionic electropolymerization layer in degradation of printing and dyeing wastewater. The invention mixes water, monomer, protonic acid, excipient and interface activator to prepare supporting electrolyte, and prepares bionic electric polymerization layer on the surface of low natural potential metal such as carbon steel, pure copper, aluminum alloy by constant potential one-step method. Based on the extremely high electric activity surface area of the bionic electric polymeric layer, the organic pollutants in the printing and dyeing wastewater can be efficiently degraded, and other pollutants (COD, dissolved solid matters and the like) can be efficiently removed through mechanisms such as electric adsorption and the like.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a method for preparing a bionic electropolymerization layer in one step by constant potential and application of the bionic electropolymerization layer in degradation of printing and dyeing wastewater.
Background
A great deal of printing and dyeing wastewater is generated when cotton, hemp, chemical fiber, silk and blended products thereof are printed or dyed. According to statistics, the water consumption is 100-200 tons per 1 ton of printed and dyed textiles, wherein more than 80 percent of water is discharged in the form of waste water. The discharged printing and dyeing wastewater mainly contains organic dye, partial dyeing assistant, oil agent, inorganic salt, fiber and other pollutants, has high Chemical Oxygen Demand (COD) and chromaticity and belongs to industrial wastewater difficult to treat. Therefore, a method for efficiently and economically treating industrial printing and dyeing wastewater is needed.
As a cleaning process, in 1969, Backnurst et al designed a fluidized Bed Electrode (FBE for Fluid Bed Electrode). Compared with a flat electrode, The electrode has higher specific surface area, and The electrolyte flows in The pore channel, thereby greatly improving The mass transfer process in The electrolytic reactor (Journal of The Electrochemical Society,1993,140: 1632-. In 1973, M.Fleischmammm F.Goodridge et al successfully developed Bipolar Packed Bed electrodes (BPBE for short) and greatly improved the efficiency of electrochemical water treatment technology (Electrochimica Acta,1977,22: 913-920).
Since Stucki and Comningella utilize DSA electrode to carry out oxidative degradation on organic matters in wastewater (Applied Electrochemistry,1991,21:14-20,99-104, 703-. At present, for the electrochemical treatment of printing and dyeing wastewater, electrodes such as modified metal oxides, boron-doped diamonds and the like are often adopted as anodes, and the printing and dyeing wastewater is treated by electrochemical oxidation to reach relevant discharge standards. Comprehensive analysis is closest to the prior art, and the aim of treating the printing and dyeing wastewater is fulfilled by using a functional electrode to treat the printing and dyeing wastewater and mainly depending on the high overpotential of an anode to carry out electrochemical oxidation to mineralize and degrade organic pollutants. However, when the dyeing wastewater is treated by electrochemical oxidation by using a modified metal oxide or the like as an anode (how faithful, etc., water treatment Technology, 2012, 38(11): 55-58; Wei Zhang, et al, Pigment & Resin Technology,2020,49(1): 46-54; Chinese patent CN110627168A), the treatment efficiency is often limited by a side reaction-oxygen evolution reaction, so that the treatment efficiency is gradually reduced along with the increase of time, and further, the energy consumption is increased. In addition, the treatment efficiency of the modified metal electrode on the printing and dyeing wastewater is very sensitive to factors such as the pH value of the environment, the temperature, the initial pollutant concentration, the treatment time and the like, the stable treatment efficiency is difficult to maintain, and other pollutants in the wastewater are difficult to treat; or as a pretreatment process, and is matched with other wastewater treatment technologies (Fenton oxidation, biological treatment, membrane separation and the like), the unique advantages of the electrochemical water treatment technology are not fully embodied.
Disclosure of Invention
Aiming at the problem that the electrodes such as modified noble metals or diamonds are difficult to maintain the efficient and stable treatment efficiency of the printing and dyeing wastewater in the prior art, the invention designs the support electrolyte, selects the proper monomer formula and dopant components, and prepares the bionic electropolymerization layer on the surface of low natural potential metals such as carbon steel, pure copper, aluminum alloy and the like by a constant potential one-step method, thereby protecting the metal substrate and efficiently degrading organic pollutants in the printing and dyeing wastewater.
The method for preparing the bionic electropolymerization layer by constant potential one step comprises the following steps:
(1) polishing the metal surface to a metallographic phase, then ultrasonically cleaning the metal surface in a mixed solvent of ethanol and acetone, and drying the metal surface under nitrogen flow;
(2) mixing water, a monomer, protonic acid, an excipient and an interfacial terminating agent to prepare a supporting electrolyte, wherein the concentration of the monomer is 0.05-0.2mol/L, the concentration of the protonic acid is 0.05-0.5mol/L, the concentration of the excipient is 0.01-0.15mol/L, and the concentration of the interfacial terminating agent is 0.01-0.1 mol/L;
(3) taking the metal treated in the step (1) as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, and carrying out in-situ polymerization on a monomer on the surface of the working electrode through a three-electrode electrochemical reaction, wherein the potential range is 0.1-0.8V, and the polymerization time is 5-30 min;
(4) and after polymerization is finished, taking out the working electrode, and carrying out vacuum drying at 40-55 ℃ to obtain the polar plate with the surface modified bionic electropolymerization layer.
The metal is one of carbon steel, pure copper and aluminum alloy.
The monomer is one or more of N-formanilide, 2-methoxyaniline, N-ethylcarbazole, beta-aminopyrrole, beta-nitropyrrole and 5-fluoroindole.
The protonic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid and oxalic acid.
The excipient is one or more of sodium salicylate, camphorsulfonic acid, cinnamic acid, carvacrol and gamma-aminobutyric acid.
The interfacial activator is one or more of sodium cinnamate, sodium gluconate and sodium tripolyphosphate.
The prepared polar plate with the surface modified bionic electropolymerization layer is applied to degradation of printing and dyeing wastewater. The specific operation of degrading the printing and dyeing wastewater is as follows: and (3) respectively taking the polar plate with the surface modified with the bionic electropolymerization layer as a cathode and an anode, wherein the distance between the cathode and the anode is 1-3cm, and treating the printing and dyeing wastewater under the voltage of 5-10V.
The bionic electropolymerization layer prepared by the invention has the following advantages:
1) the one-step preparation method has the advantages of simple and convenient process, mild reaction, no monomer reduction process, high efficiency and controllability;
2) the monomer in the prepared supporting electrolyte is electropolymerized on the surface of the metal in one step to obtain a bionic structure, and the bionic electropolymerization layers with different electroactive surface areas can be obtained by adjusting the types and the concentrations of the monomer, the protonic acid, the excipient and the interfacial terminating agent in the supporting electrolyte;
3) based on the extremely high electric activity surface area of the bionic electric polymeric layer, the organic pollutants in the printing and dyeing wastewater can be efficiently degraded, and other pollutants (COD, dissolved solid matters and the like) can be efficiently removed through mechanisms such as electric adsorption and the like.
Drawings
FIG. 1 is an electropolymerized coral-like poly (formanilide) layer prepared on the surface of 20# carbon steel in example 1.
FIG. 2 shows a poly-N-ethyl carbazole electro-polymerized layer with a leaf-like structure prepared on the surface of 1350 aluminum alloy in example 3.
FIG. 3 shows an electropolymerized layer of rose-like poly beta-aminopyrrole prepared on the surface of 20# carbon steel in example 4.
Detailed Description
Example 1
Using 20# carbon steel as a working electrode (5cm multiplied by 5cm), grinding the working electrode to a mirror surface by using 400, 800, 1000 and 2000-mesh silicon carbide waterproof sand paper in sequence, cleaning the working electrode in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally drying the working electrode at 25 ℃ under a nitrogen flow for later use.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.05mol/L of N-formanilide, 0.3mol/L of sulfuric acid, 0.15mol/L of camphorsulfonic acid and 0.01mol/L of sodium cinnamate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 10min under the constant voltage of 0.2V (relative to the reference electrode), taking out and drying in vacuum at 40 ℃ to obtain the coral-like structure poly-N-formanilide layer (shown in figure 1).
20# carbon steel with the surface modified with poly-N-formanilide is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 3cm, the indigo-containing wastewater (800 mg/L of indigo and 1g/L of dissolved solid) is dynamically and continuously treated for 150min (the water inflow rate is 120L/h) under the 5V direct current, the decolorization rate reaches 99.82%, and the removal rate of the dissolved solid is 90.33%.
Example 2
Pure copper is taken as a working electrode (5cm multiplied by 5cm), silicon carbide waterproof sand paper of 400 meshes, 800 meshes, 1000 meshes and 2000 meshes is sequentially used for polishing to a mirror surface, the mirror surface is cleaned in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally the mirror surface is dried under nitrogen flow at 25 ℃ for standby.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.2mol/L of 2-anisidine, 0.05mol/L of hydrochloric acid, 0.01mol/L of sodium salicylate and 0.1mol/L of sodium gluconate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 5min under the constant voltage of 0.8V (relative to the reference electrode), taking out and vacuum-drying at 55 ℃ to obtain the cauliflower-like poly-2-anisidine layer.
Pure copper with the surface modified poly (2-methoxyaniline) is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 1cm, under the direct current voltage of 10V, the wastewater containing rhodamine B (containing rhodamine B1g/L and dissolved solids are 1.5g/L) is dynamically and continuously treated for 30min (the water inflow rate is 120L/h), the decolorization rate reaches 98.90 percent, and the removal rate of the dissolved solids is 89.90 percent.
Example 3
Using 1350 aluminium alloy as working electrode (5cm × 5cm), polishing to mirror surface with 400, 800, 1000, 2000 mesh silicon carbide waterproof sand paper, cleaning in 1/1 volume ratio ultrasonic bath of ethanol/acetone mixture, and drying at 25 deg.C under nitrogen flow.
The working electrode is immersed into 300mL of supporting electrolyte (containing 0.1mol/L of N-ethyl carbazole, 0.5mol/L of nitric acid, 0.1mol/L of cinnamic acid and 0.08mol/L of sodium tripolyphosphate), a saturated calomel electrode is taken as a reference electrode, a platinum wire is taken as an auxiliary electrode, polymerization is carried out for 30min under the constant voltage of 0.1V (relative to the reference electrode), and the working electrode is taken out and dried in vacuum at the temperature of 45 ℃ to obtain the poly-N-ethyl carbazole layer with the imitated leaf structure (shown in figure 2).
The aluminum alloy with the surface modified poly-N-ethyl carbazole is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 2cm, under 6V direct current voltage, methyl red-containing wastewater (containing 500mg/L of methyl red and 800mg/L of dissolved solid) is dynamically and continuously treated for 120min (water inflow rate: 120L/h), the decolorization rate reaches 91.12%, and the removal rate of the dissolved solid is 93.83%.
Example 4
Using 20# carbon steel as a working electrode (5cm multiplied by 5cm), grinding the working electrode to a mirror surface by using 400, 800, 1000 and 2000-mesh silicon carbide waterproof sand paper in sequence, cleaning the working electrode in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally drying the working electrode at 25 ℃ under a nitrogen flow for later use.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.15mol/L of beta-aminopyrrole, 0.5mol/L of oxalic acid, 0.09mol/L of carvacrol and 0.05mol/L of sodium cinnamate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 15min under the constant voltage of 0.6V (relative to the reference electrode), taking out and drying in vacuum at 50 ℃ to obtain the rose-like structure poly-beta-aminopyrrole layer (shown in figure 3).
Carbon steel with surface modified poly beta-aminopyrrole is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 2cm, the indigo-containing wastewater (containing 800mg/L of indigo and 1g/L of dissolved solid) is dynamically and continuously treated for 120min (water inflow rate: 120L/h) under 8V direct current, the decolorization rate reaches 97.08%, and the removal rate of the dissolved solid is 91.92%.
Example 5
Pure copper is taken as a working electrode (5cm multiplied by 5cm), silicon carbide waterproof sand paper of 400 meshes, 800 meshes, 1000 meshes and 2000 meshes is sequentially used for polishing to a mirror surface, the mirror surface is cleaned in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally the mirror surface is dried under nitrogen flow at 25 ℃ for standby.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.1mol/L of beta-nitropyrrole, 0.1mol/L of hydrochloric acid, 0.12mol/L of gamma-aminobutyric acid and 0.08mol/L of sodium gluconate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 20min under the constant voltage of 0.5V (relative to the reference electrode), taking out and drying in vacuum at 45 ℃ to obtain the poly-beta-nitropyrrole layer with the coral-like structure.
Pure copper with surface modified poly beta-nitropyrrole is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 3cm, the indigo-containing wastewater (containing 800mg/L of indigo and 1g/L of dissolved solid) is dynamically and continuously treated for 40min (the water inflow rate is 120L/h) under 10V direct current, the decolorization rate reaches 98.20%, and the removal rate of the dissolved solid is 95.07%.
Example 6
Using 2024 aluminum alloy as working electrode (5cm × 5cm), polishing with 400, 800, 1000, 2000 mesh silicon carbide waterproof sand paper to mirror surface, cleaning in 1/1 (volume ratio) ultrasonic bath of ethanol/acetone mixture, and drying at 25 deg.C under nitrogen flow.
The working electrode is immersed into 300mL of supporting electrolyte (containing 0.15mol/L of 5-fluoroindole, 0.15mol/L of sulfuric acid, 0.1mol/L of sodium salicylate and 0.08mol/L of sodium tripolyphosphate), a saturated calomel electrode is taken as a reference electrode, a platinum wire is taken as an auxiliary electrode, polymerization is carried out for 10min under the constant voltage of 0.8V (relative to the reference electrode), and the working electrode is taken out and dried in vacuum at the temperature of 40 ℃ to obtain the coral-like structure poly-5-fluoroindole layer.
The aluminum alloy with the surface modified with poly-5-fluoroindole is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 1cm, the indigo-containing wastewater (containing 800mg/L of indigo and 1g/L of dissolved solid) is dynamically and continuously treated for 30min (the water inflow rate is 120L/h) under the 5V direct current, the decolorization rate reaches 97.75 percent, and the removal rate of the dissolved solid is 90.23 percent.
Example 7
Using EH36 carbon steel as a working electrode (5cm multiplied by 5cm), polishing to a mirror surface by using 400, 800, 1000 and 2000 mesh silicon carbide waterproof sand paper in sequence, cleaning in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally drying under 25 ℃ nitrogen flow for later use.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.05mol/L of N-formanilide, 0.15mol/L of 5-fluoroindole, 0.5mol/L of oxalic acid, 0.05mol/L of camphorsulfonic acid, 0.05mol/L of sodium salicylate, 0.02mol/L of sodium cinnamate and 0.06mol/L of sodium tripolyphosphate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 10min under the constant voltage of 0.8V (relative to the reference electrode), taking out and drying in vacuum at 40 ℃ to obtain the 5-fluoroindole layer and the N-formanilide copolymerization layer with the rose-like structure.
Carbon steel with a surface modified by a 5-fluoroindole and N-formanilide copolymerization layer is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 3cm, under 7V direct current voltage, wastewater containing rhodamine B (containing rhodamine B1g/L and 1.5g/L of dissolved solids) is dynamically and continuously treated for 50min (water inflow rate: 120L/h), and the decolorization rate reaches 99.12%; the dissolved solids removal was 92.18%.
Example 8
Pure copper is taken as a working electrode (5cm multiplied by 5cm), silicon carbide waterproof sand paper of 400 meshes, 800 meshes, 1000 meshes and 2000 meshes is sequentially used for polishing to a mirror surface, the mirror surface is cleaned in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally the mirror surface is dried under nitrogen flow at 25 ℃ for standby.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.1mol/L of N-ethyl carbazole, 0.1mol/L of beta-aminopyrrole, 0.2mol/L of oxalic acid, 0.1mol/L of sulfuric acid, 0.1mol/L of carvacrol, 0.05mol/L of gamma-aminobutyric acid and 0.05mol/L of sodium gluconate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 30min under the constant voltage of 0.5V (relative to the reference electrode), taking out and drying in vacuum at 50 ℃ to obtain the dendriform N-ethyl carbazole and beta-aminopyrrole copolymerized layer.
Pure copper with a surface modified with an N-ethyl carbazole and beta-aminopyrrole copolymerization layer is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 2cm, under 10V direct current voltage, methyl red-containing wastewater (containing 500mg/L of methyl red and 800mg/L of dissolved solid) is dynamically and continuously treated for 100min (water inflow rate: 120L/h), and the decolorization rate reaches 99.50%; the removal rate of dissolved solids was 98.33%.
Example 9
Using 20# carbon steel as a working electrode (5cm multiplied by 5cm), grinding the working electrode to a mirror surface by using 400, 800, 1000 and 2000-mesh silicon carbide waterproof sand paper in sequence, cleaning the working electrode in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally drying the working electrode at 25 ℃ under a nitrogen flow for later use.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.1mol/L of N-formanilide, 0.1mol/L of 2-methoxyaniline, 0.3mol/L of oxalic acid, 0.2mol/L of nitric acid, 0.05mol/L of carvacrol, 0.05mol/L of camphorsulfonic acid and 0.05mol/L of sodium tripolyphosphate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 10min under the constant voltage of 0.8V (relative to the reference electrode), taking out and drying in vacuum at 40 ℃ to obtain the rose-like structure copolymerized layer of N-ethylcarbazole and beta-aminopyrrole.
Carbon steel with surface modified N-formanilide and 2-methoxyaniline copolymerization layers is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 1cm, the indigo-containing wastewater (containing 800mg/L of indigo and 1g/L of dissolved solid) is dynamically and continuously treated for 40min (the water inflow rate is 120L/h) under 5V direct current voltage, and the decolorization rate reaches 98.35 percent; the removal rate of dissolved solids was 95.13%.
Example 10
Using 2219 aluminum alloy as a working electrode (5cm multiplied by 5cm), sequentially using 400, 800, 1000 and 2000-mesh silicon carbide waterproof sand paper to polish the working electrode to a mirror surface, cleaning the working electrode in an ultrasonic bath of 1/1 (volume ratio) ethanol/acetone mixed solution, and finally drying the working electrode at 25 ℃ under nitrogen flow for later use.
Immersing a working electrode into 300mL of supporting electrolyte (containing 0.1mol/L of N-formanilide, 0.1mol/L of beta-nitropyrrole, 0.3mol/L of sulfuric acid, 0.05mol/L of gamma-aminobutyric acid, 0.05mol/L of camphorsulfonic acid, 0.05mol/L of sodium cinnamate and 0.05mol/L of sodium gluconate), using a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, polymerizing for 10min under the constant voltage of 0.6V (relative to the reference electrode), taking out and drying in vacuum at 40 ℃ to obtain the dendrigraft-like structure N-formanilide and beta-nitropyrrole copolymerized layer.
Aluminum alloy with surface modified with N-formanilide and beta-nitropyrrole copolymer layers is respectively used as a cathode plate and an anode plate, the distance between the cathode and the anode is 3cm, the indigo-containing wastewater (containing 800mg/L of indigo and 1g/L of dissolved solid) is dynamically and continuously treated for 150min (the water inflow rate is 120L/h) under 5V direct current voltage, and the decolorization rate reaches 99.02 percent; the dissolved solids removal was 94.19%.
Claims (8)
1. A method for preparing a bionic electropolymerization layer by constant potential in one step is characterized by comprising the following specific steps:
(1) polishing the metal surface to a metallographic phase, then ultrasonically cleaning the metal surface in a mixed solvent of ethanol and acetone, and drying the metal surface under nitrogen flow;
(2) mixing water, a monomer, protonic acid, an excipient and an interfacial terminating agent to prepare a supporting electrolyte, wherein the concentration of the monomer is 0.05-0.2mol/L, the concentration of the protonic acid is 0.05-0.5mol/L, the concentration of the excipient is 0.01-0.15mol/L, and the concentration of the interfacial terminating agent is 0.01-0.1 mol/L;
(3) taking the metal treated in the step (1) as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum wire as an auxiliary electrode, and carrying out in-situ polymerization on a monomer on the surface of the working electrode through a three-electrode electrochemical reaction, wherein the potential range is 0.1-0.8V, and the polymerization time is 5-30 min;
(4) and after polymerization is finished, taking out the working electrode, and carrying out vacuum drying at 40-55 ℃ to obtain the polar plate with the surface modified bionic electropolymerization layer.
2. The method of claim 1, wherein the metal is one of carbon steel, pure copper, and an aluminum alloy.
3. The method according to claim 1, wherein the monomer is one or more of formanilide, 2-methoxyaniline, N-ethylcarbazole, β -aminopyrrole, β -nitropyrrole, and 5-fluoroindole.
4. The method according to claim 1, wherein the protonic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid and oxalic acid.
5. The method of claim 1, wherein the excipient is one or more of sodium salicylate, camphorsulfonic acid, cinnamic acid, carvacrol, and gamma-aminobutyric acid.
6. The method of claim 1, wherein the interfacial activator is one or more of sodium cinnamate, sodium gluconate, and sodium tripolyphosphate.
7. The application of the polar plate with the surface modified bionic electropolymerization layer prepared by the method of claim 1 in degrading printing and dyeing wastewater.
8. The application of claim 7, wherein the specific operation of degrading the printing and dyeing wastewater is as follows: and (3) respectively taking the polar plate with the surface modified with the bionic electropolymerization layer as a cathode and an anode, wherein the distance between the cathode and the anode is 1-3cm, and treating the printing and dyeing wastewater under the voltage of 5-10V.
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| CN104878406A (en) * | 2015-05-20 | 2015-09-02 | 浙江大学 | Method for electrochemical synthesis of petal-shaped nano structure polyaniline |
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| CN103137334A (en) * | 2011-12-01 | 2013-06-05 | 上海奥威科技开发有限公司 | Manufacture method of electrode slice of supercapacitor and supercapacitor |
| CN104878406A (en) * | 2015-05-20 | 2015-09-02 | 浙江大学 | Method for electrochemical synthesis of petal-shaped nano structure polyaniline |
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| 中国化工防治污染技术协会: "《化工废水处理技术》", 30 April 2000, 北京：化学工业出版社 * |
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