CN113562812A - Preparation method and application of composite electrode for treating high-chlorine organic wastewater - Google Patents
Preparation method and application of composite electrode for treating high-chlorine organic wastewater Download PDFInfo
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- 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
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- 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
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F2001/46138—Electrodes comprising a substrate and a coating
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- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention relates to a preparation method of a composite electrode for treating high-chlorine organic wastewater, which comprises the following steps: s1, after the carbon fiber cloth is decontaminated, deoiled and cleaned, acid oxidation is carried out, and oxygen-containing hydrophilic groups are formed on the surface of the carbon fiber cloth to make the carbon fiber cloth hydrophilic; s2, electrodeposition: respectively taking carbon fiber cloth as an anode and a cathode, taking an aqueous solution of ruthenium salt as electrodeposition liquid, and electrifying electrodeposition to obtain a Ru/CFS electrode on the cathode side; s3, roasting: the Ru/CFS electrode is washed by water, dried and roasted at the temperature of 150-350 ℃ in oxygen-containing atmosphere to obtain RuO2a/CFS electrode; s4, electrodeposition: carbon fiber cloth is used as an anode, and RuO is used2Taking a/CFS electrode as a cathode, taking an aqueous solution of manganese salt as an electrodeposition solution, electrifying electrodeposition to obtain Mn-RuO on the cathode side2a/CFS electrode; s5, roasting: adding Mn-RuO2The CFS electrode is washed by water, dried and roasted at the temperature of 150-350 ℃ in oxygen-containing atmosphere to obtain the high-chlorine treated electrodeMnO of machine waste water2‑RuO2a/CFS composite electrode. The invention solves the problems that the surface of the electrode is easy to generate cracks, the electrode is easy to passivate, the treatment efficiency of chloride ions is not high, and the like.
Description
Technical Field
The invention relates to the technical field of electrochemical inorganic materials, in particular to a preparation method and application of a composite electrode for treating high-chlorine organic wastewater.
Background
The high-chlorine organic wastewater refers to organic wastewater containing high-concentration chloride ions, contains organic pollutants and a large amount of inorganic salts, and can be produced in production processes of synthetic rubber factories, pharmaceutical factories, dyes, chemical engineering and the like in the industrial production process. The high-chlorine organic wastewater has wide sources, large water quantity and complex components, brings serious harm to human bodies, fishes and crops in water bodies, and is difficult to degrade by directly utilizing a biochemical method and an evaporation method. Therefore, how to efficiently and cleanly treat the high-chlorine organic wastewater is a very urgent task.
Due to the particularity of the high-chlorine organic wastewater, the current treatment method is difficult to meet the requirements, and the new process and the new method have great significance in development and research. The electrochemical method is a novel green pollution-free water treatment method, has no special requirements on the salinity of a water body, and can increase the conductivity of the wastewater to be treated and reduce the energy consumption due to the existence of free ions. And the electrochemical method can also fully utilize chloride ions in the high-chlorine wastewater, the chloride ions are converted into active chlorine in the electrochemical treatment process, and the active chlorine has strong oxidizing property and can oxidize organic matters to achieve the purpose of degradation and removal. The electrochemical method has no limit requirement on salt content, does not need to be diluted by adding water, saves water resources and has low cost, so the electrochemical method has advantages in the field of treating high-chlorine organic wastewater.
The electrode material is the core of the electrocatalysis technology, the anode electrode (generally coated with metal oxide on a conductive current collector) which is a traditional material is mostly applied at present, the common manufacturing method is a hydrothermal decomposition method or a sol-gel method, the two preparation methods can cause the surface of the electrode to form cracks in the using process, electrolyte can permeate into the surface of a carrier along the cracks, the electrode generates a passivation phenomenon, and the charge transfer between an active substance on the surface of the electrode and the carrier is blocked, so that the electrochemical performance of the electrode is influenced. Therefore, the provision of new matrix materials or new preparation methods is of great significance for the development of electrode materials.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a composite electrode for treating high-chlorine organic wastewater, so as to solve the problems that cracks are easily generated on the surface of the electrode, the electrode is easily passivated, and the treatment efficiency of chloride ions is not high.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a preparation method of a composite electrode for treating high-chlorine organic wastewater comprises the following steps:
s1, pretreatment of the carbon fiber cloth: after the carbon fiber cloth is decontaminated, deoiled and cleaned, acid oxidation is carried out, and oxygen-containing hydrophilic groups are formed on the surface of the carbon fiber cloth, so that the carbon fiber cloth has hydrophilicity;
s2, first-step electrodeposition: respectively taking the carbon fiber cloth prepared in the step S1 as an anode and a cathode, taking an aqueous solution of ruthenium salt as electrodeposition liquid, and carrying out electrodeposition to obtain a Ru/CFS electrode on the cathode side;
s3, first-step roasting: the Ru/CFS electrode is washed by deionized water, dried and roasted at the temperature of 150-350 ℃ in oxygen-containing atmosphere to obtain RuO2a/CFS electrode;
s4, second-step electrodeposition: the carbon fiber cloth prepared in step S1 is used as an anode, RuO is used2Taking a/CFS electrode as a cathode, taking an aqueous solution of manganese salt as an electrodeposition solution, electrifying electrodeposition to obtain Mn-RuO on the cathode side2a/CFS electrode;
s5, second-step roasting: adding Mn-RuO2the/CFS electrode is washed and dried by deionized water and is roasted at the temperature of 150 ℃ and 350 ℃ in oxygen-containing atmosphere to obtain MnO for treating high-chlorine organic wastewater2-RuO2a/CFS composite electrode.
According to the preferred embodiment of the present invention, the method of S1 is: ultrasonically cleaning carbon fiber cloth by using deionized water, absolute ethyl alcohol and acetone, placing the carbon fiber cloth into mixed concentrated acid of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:1, heating for 1-2h, and drying for later use.
Wherein, the drying conditions are as follows: air-blast drying is carried out for 5-8h at the temperature of 105-120 ℃.
According to the preferred embodiment of the present invention, the preparation method of the S2 electrodeposition solution comprises: dissolving soluble ruthenium salt or hydrate thereof, concentrated hydrochloric acid and KCl/sodium chloride in deionized water, and uniformly mixing and stirring to obtain electrodeposition liquid; wherein the soluble ruthenium salt is RuCl3、Ru(NO)3Or Ru2(SO4)3。
According to the preferred embodiment of the present invention, the concentration of each ion in the electrodeposition solution in S2 is: ru3+:0.05～0.06mol/L，Cl-:0.01～0.025mol/L，K+:0.010～0.015mol/L。
According to a preferred embodiment of the present invention, the preparation method of the electrodeposition solution in S4 comprises: dissolving soluble manganese salt or hydrate thereof, concentrated hydrochloric acid and KCl/sodium chloride in deionized water, and uniformly mixing and stirring to obtain electrodeposition liquid; wherein the soluble manganese salt is manganese nitrate or manganese chloride.
According to the preferred embodiment of the present invention, the concentration of each ion in the electrodeposition solution in S4 is:
Mn2+:0.1～0.2mol/L，Cl-:0.015～0.030mol/L，K+:0.010～0.015mol/L。
according to a preferred embodiment of the present invention, the current density is 20 to 25mA cm when performing the electrodeposition reaction in S2-2The electrodeposition time is 35 min-1 h.
When preparing the electrodeposition liquid, the main function of adding KCl/NaCl is to increase the conductivity of the electrodeposition liquid, save energy consumption, and prevent the influence of too small conductivity, high energy consumption and too slow reaction speed on the stacking density of metal atoms on the CFS; the main effect of adding concentrated hydrochloric acid HCl is to increase the H + concentration, so that the solution is kept acidic, and the phenomenon that the metal ions generate hydroxide precipitates to influence the electrode loading effect along with the reaction is avoided.
According to the preferred embodiment of the present invention, the drying conditions of S3 and S5 are as follows: drying by blowing at 50-65 deg.C for 6-8 hr.
According to the preferred embodiment of the present invention, the baking in S3 and S5 is performed in an air atmosphere, and the temperature rising rate during the baking is 60-70 ℃/h.
In a second aspect, the invention provides a method for treating high-chlorine organic wastewater, wherein an electrolysis device consisting of a composite electrode prepared in any one of the above embodiments as an anode and carbon fiber cloth with the same size as the anode is used for electrolyzing the organic wastewater, the current is 0.15V-3V, and the electrifying time is 0.5-3 h.
Preferably, NaCl is added to the organic waste water before the electrolysis is performed so that the concentration of NaCl in the organic waste water is 25 to 40 g/L. Preferably, the organic wastewater is an organic wastewater containing methylene blue. Preferably, the concentration of the methylene blue in the organic wastewater is 40-60mg/L, and the COD of the organic wastewater is 100-200 mg/L.
In general, the organic waste water to be treated may contain no chlorine or only a small amount of chlorine, and in this case, a commonly available electrolyte such as sodium chloride is added to increase the chlorine content of the organic waste water.
MnO prepared by the invention2-RuO2the/CFS composite electrode is used as an anode and can catalyze and reduce Cl in organic wastewater-The active chlorine is active chlorine, has strong oxidizing property, and can oxidize and degrade organic matters (such as methylene blue and the like) in the organic wastewater in situ, thereby reducing the COD value of the wastewater.
(III) advantageous effects
Compared with the prior art, the invention has the following technical effects:
(1) the invention uses carbon fiber cloth as a matrix material to load RuO2And MnO2The carbon fiber cloth is a braided fabric obtained by weaving carbon fibers, the surface of the carbon fiber cloth is provided with three-dimensional textures, the three-dimensional textures comprise special structures such as a slender cylindrical fiber surface, fine gaps among fibers, and arches and depressions at the overlapped part of fiber bundles, so that the active surface area and the catalytic capacity of the composite electrode can be obviously improved, and the number of active sites on the surface of the composite electrode is greatly increasedAnd the electrochemical reaction rate is effectively improved. Compared with the traditional DSA electrode and Ti-based composite electrode, the carbon fiber cloth with the three-dimensional net structure can be tightly combined with the active component, so that no crack is formed on the surface of the metal oxide layer.
(2) The invention adopts an electrodeposition method to successively load RuO2And MnO2The loading method is simple and the type and the loading capacity are controllable; ru and Mn are respectively stacked on the surface of CFS serving as a cathode in a single atom form in the loading process, and the stacking of metal atoms has the advantages of three-dimensional property, large surface area and strong catalytic activity. Among them, RuO of CFS surface2And MnO2The two catalytic performances are cooperated, and compared with active metal with a single component, the chlorine evolution performance can be obviously improved, and the removal rate of methylene blue and COD is improved. RuO2And MnO2Solid solution can be formed between the two electrodes, corrosion of corrosive acid and alkali or electrolyte is prevented, diffusion of oxidizing substances and corrosive electrolyte is effectively prevented, the service life of the electrode is longer, and chlorine evolution efficiency can be improved.
(3) The invention uses CFS as a substrate and adopts an electrodeposition method to load RuO firstly2Reloading MnO2MnO prepared by the step-by-step loading method2-RuO2Compared with an electrode prepared by a codeposition method (the ions of Ru and Mn are simultaneously contained in the electrodeposition solution), the/CFS composite electrode has better electrocatalytic activity under the same other conditions.
(4) Compared with a composite electrode taking Ti as a base material, the composite electrode takes CFS as the base material, and TiO formed between the electrode active material layer and the interface of the base material does not occur2Passivation film, etc., and further causes the efficiency of chlorine evolution to be reduced.
(5) The preparation method is simple, the adopted carbon fiber cloth belongs to common industrial materials, the industrial application prospect is good, the catalytic performance can be greatly improved through simple acid-base treatment, and the preparation method is a reliable electrode preparation process in the field of water treatment.
Drawings
FIG. 1 shows a wide-angle XRD spectrum (RuO) of a carbon fiber cloth and samples obtained in examples 1, 2 and 32、MnO2Standard card contrast)
FIGS. 2 and 3 are scanning electron micrographs of the pretreated pure carbon fiber cloth of example 1 under different magnification.
FIGS. 4 and 5 show RuO as an electrode sample obtained in example 22Scanning electron microscopy of/CFS.
FIGS. 6 and 7 show MnO as electrode samples obtained in example 32-RuO2Scanning electron microscopy of/CFS.
FIG. 8 is a cyclic voltammogram of the electrode samples obtained in example 1, example 2, and example 3.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
In this example, a pure carbon fiber cloth electrode is prepared by the following steps:
(1) cutting off 2 x 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous ethanol and ultrapure water for 35min, respectively, removing soluble impurities, cleaning with deionized water for multiple times, and naturally drying at room temperature to obtain A/CFS.
(2) The A/CFS was placed in 50ml of mixed acid (concentrated H)2SO4With HNO3According to the volume ratio of 1: 1) heating and boiling for 1 hour by an electric furnace, taking out the carbon cloth for cooling, washing the carbon cloth by a large amount of deionized water until no acidity exists, and then carrying out forced air drying for 6 hours at 120 ℃ in a forced air drying box to obtain a pure carbon fiber cloth electrode.
Example 2
This example prepares RuO2the/CFS composite electrode comprises the following steps:
(1) cutting off 2 x 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous ethanol and ultrapure water for 35min, respectively, removing soluble impurities, cleaning with deionized water for multiple times, and naturally drying at room temperature to obtain A/CFS.
(2) The A/CFS was placed in 50ml of mixed acid (concentrated H)2SO4With HNO3According to the volume ratio of 1: 1) boiling in an electric furnace for 1 hour, taking out the carbon cloth, cooling, and washing with deionized water until no acidityThen, the mixture was air-dried at 120 ℃ for 6 hours in an air-drying oven to obtain B/CFS.
(3) 0.1307g of RuCl were weighed out3·3H2O is dissolved in 100ml of deionized water, and 12.5ul of concentrated hydrochloric acid and 1.1238g of KCl are added, mixed evenly and stirred to obtain a mixed solution C.
(4) Taking 40ml of solution C in an electrolytic bath as an electro-deposition solution, taking B/CFS as a cathode, and setting the current density at 25mA/cm2And electrifying for electrodeposition for 35min to obtain the D/CFS.
(5) Washing the D/CFS with deionized water, drying, and roasting the sample in a tubular furnace at 350 ℃ for 5h in the air atmosphere to obtain the RuO2a/CFS electrode.
Comparative example 1
This comparative example uses an activated carbon plate as a substrate to prepare RuO2The composite active carbon electrode is used as a reference, and the preparation method of the composite electrode comprises the following steps:
(1) cutting an activated carbon plate prepared by 2 x 2cm in size, ultrasonically cleaning the activated carbon plate in acetone, absolute ethyl alcohol and ultrapure water for 35min respectively, washing out soluble impurities, then cleaning the activated carbon plate for multiple times by using deionized water, and naturally airing the activated carbon plate at room temperature for later use to obtain A/CFS.
(2) Weighing 0.1307 gGluCl3·3H2O is dissolved in 100ml of deionized water, and 12.5ul of concentrated hydrochloric acid and 1.1238g of KCl are added, mixed evenly and stirred to obtain a mixed solution B.
(3) Taking 40ml of the solution B and an electrolytic bath as an electro-deposition solution, taking a pretreated electrode A as a cathode, and setting the current density at 25mA/cm2And electrifying for electrodeposition for 35min to obtain C/CFS.
(4) Washing and drying the C/CFS by using deionized water, and then roasting the sample in a tubular furnace air atmosphere at 350 ℃ for 5 hours to obtain the RuO2And (3) compounding an active carbon electrode.
Respectively with RuO of comparative example 12Composite activated carbon electrode, pure carbon fiber cloth of example 1 and RuO of example 22the/CFS electrode is an anode, the carbon fiber cloth with the same size is a cathode to form an electrolysis device, the voltage is 1.5V, the current is 0.15A, the NaCl concentration of the electrolyte is 15g/L, and the electrifying electrolysis time is 30min, test results are shown in Table 1.
Table 1:
| examples | Electrode for electrochemical cell | Methylene blue removal rate/%) | COD removal rate/%) |
| Example 1 | Pure carbon fiber cloth | 49.58％ | 32.55％ |
| Example 2 | RuO2/CFS | 86.23％ | 60.52％ |
| Comparative example 1 | RuO2Composite active carbon electrode | 62.82％ | 48.42％ |
As can be seen from Table 1, the RuO produced in example 22The removal rate of the/CFS electrode to methylene blue and COD is higher than that of the traditional RuO2The composite active carbon electrode and the unmodified pure carbon fiber cloth electrode in the market are greatly improved. This is because the three-dimensional network carbon fiber cloth is used as a base material, as opposed to a carbon fiber clothFor the traditional activated carbon material, the attachment area of the active sites can be increased, and the electrocatalytic reaction rate is improved. Therefore, the method can show the superiority of preparing the composite electrode by taking CFS as a matrix and combining the electro-deposition technology and the metal oxide loading technology.
Example 3
Preparation of MnO in this example2-RuO2the/CFS composite electrode comprises the following steps:
(1) cutting off 2 x 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous ethanol and ultrapure water for 35min, respectively, removing soluble impurities, cleaning with deionized water for multiple times, and naturally drying at room temperature to obtain A/CFS.
(2) The A/CFS was placed in 50ml of mixed acid (concentrated H)2SO4With HNO3According to the volume ratio of 1: 1) in the water solution, heating and boiling for 1 hour by an electric furnace, taking out the carbon cloth for cooling, washing the carbon cloth by a large amount of deionized water until no acidity exists, and then carrying out forced air drying for 6 hours at 120 ℃ in a forced air drying box to obtain B/CFS.
(3) 0.1970g (0.01mol) of MnCl are taken2·4H2O is dissolved in 100ml of deionized water, 89.9ul of concentrated hydrochloric acid and 0.7492g of KCl are added, and the mixture is uniformly mixed and stirred to obtain a uniformly mixed solution C.
(4) 40ml of solution C was taken as an electrodeposition solution in an electrolytic bath, RuO prepared according to the method of example 22the/CFS electrode was used as cathode and the current density was set at 25mA/cm2And electrifying for electrodeposition for 35min to obtain the D/CFS.
(5) Washing the D/CFS with deionized water, drying, and roasting the sample in a tubular furnace at 350 ℃ for 5h in the air atmosphere to obtain MnO2-RuO2the/CFS composite electrode (recorded as electrode # 1).
The pure carbon fiber cloth of example 1 and RuO prepared in example 2 were observed by an X-ray diffractometer2/CFS electrode and MnO prepared in example 32-RuO2Component structure of/CFS electrode coating. As shown in fig. 1. Wherein, MnO prepared in example 32-RuO2The X-ray diffraction intensity of the/CFS electrode coating is maximum, and MnO can be detected2And RuO2A two-phase metal oxide; thereby making it possible to explainMnO2And RuO2The active component of the metal oxide nano-particles can be better loaded on the carbon fiber cloth substrate, and the loading effect is better. As can be seen from FIG. 1, the XRD spectrogram shows that the structure of the carbon fiber cloth is not damaged after the active component Ru is loaded, and the structure is compared with RuO2The standard XRD spectrum can confirm that Ru is RuO2Active component of CFS electrode.
The pure carbon fiber cloth of example 1 and RuO prepared in example 2 were observed by a scanning electron microscope2/CFS electrode and MnO prepared in example 32-RuO2Surface topography of CFS electrodes.
As shown in fig. 2-3, the surface of the pure carbon fiber cloth is a braided fabric formed by interweaving a plurality of carbon fibers, and the surface of the pure carbon fiber cloth is three-dimensional texture, and the three-dimensional texture comprises special structures such as a slender cylindrical fiber surface, fine gaps among fibers, and bulges and depressions at the overlapped part of fiber bundles. The surface of the carbon fiber cloth has huge specific surface area and microscopic three-dimensional structure which are not possessed by a common electrode matrix (such as a Ti matrix), so that the active surface area and the catalytic capability of the composite electrode can be obviously improved.
As shown in FIGS. 4 and 5, RuO is an electrode sample obtained in example 22Scanning electron microscopy of/CFS. As shown in FIGS. 6 and 7, MnO was added to the electrode sample obtained in example 32-RuO2Scanning electron microscopy of/CFS. As can be seen in connection with FIGS. 4-7, RuO2MnO distributed on the surface of CFS at intervals in a fine-velvet state2Then embedded in RuO in granular form2In the gap of (1), overall presents RuO2Particles and MnO2The particles are embedded with each other, and the surface of the carbon fiber cloth is uniformly loaded with spherical MnO2After the particles are formed, the surfaces of the particles are rougher, the active potential surface area is larger, and the catalytic activity is stronger. The method is determined to well load multiple active metal components to obtain well-prepared MnO2-RuO2a/CFS electrode.
Example 4
Preparation of MnO in this example2-RuO2the/CFS composite electrode comprises the following steps:
(1) cutting off 2 x 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous ethanol and ultrapure water for 35min, respectively, removing soluble impurities, cleaning with deionized water for multiple times, and naturally drying at room temperature to obtain A/CFS.
(2) The A/CFS was placed in 50ml of mixed acid (concentrated H)2SO4With HNO3According to the volume ratio of 1: 1) in the water solution, heating and boiling for 1 hour by an electric furnace, taking out the carbon cloth for cooling, washing the carbon cloth by a large amount of deionized water until no acidity exists, and then carrying out forced air drying for 6 hours at 120 ℃ in a forced air drying box to obtain B/CFS.
(3) 0.9895g (0.05mol) of MnCl are taken2·4H2O is dissolved in 100ml of deionized water, 89.9ul of concentrated hydrochloric acid and 0.7492g of KCl are added, and the mixture is uniformly mixed and stirred to obtain a uniformly mixed solution C.
(4) 40ml of solution C was taken as an electrodeposition solution in an electrolytic bath, RuO prepared according to the method of example 22the/CFS electrode was used as cathode and the current density was set at 25mA/cm2And electrifying for electrodeposition for 35min to obtain the D/CFS.
(5) Washing the D/CFS with deionized water, drying, and roasting the sample in a tubular furnace at 350 ℃ for 5h in the air atmosphere to obtain MnO2-RuO2the/CFS composite electrode (recorded as electrode # 2).
Example 5
Preparation of MnO in this example2-RuO2the/CFS composite electrode comprises the following steps:
(1) cutting off 2 x 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous ethanol and ultrapure water for 35min, respectively, removing soluble impurities, cleaning with deionized water for multiple times, and naturally drying at room temperature to obtain A/CFS.
(2) The A/CFS was placed in 50ml of mixed acid (concentrated H)2SO4With HNO3According to the volume ratio of 1: 1) in the water solution, heating and boiling for 1 hour by an electric furnace, taking out the carbon cloth for cooling, washing the carbon cloth by a large amount of deionized water until no acidity exists, and then carrying out forced air drying for 6 hours at 120 ℃ in a forced air drying box to obtain B/CFS.
(3) 1.9701g (0.10mol) of MnCl are taken2Dissolving 4H2O in 100ml of deionized water, adding 89.9ul of concentrated hydrochloric acid and 0.7492g of KCl, mixing and stirringStirring to obtain a uniformly mixed solution C.
(4) 40ml of solution C was taken as an electrodeposition solution in an electrolytic bath, RuO prepared according to the method of example 22the/CFS electrode was used as cathode and the current density was set at 25mA/cm2And electrifying for electrodeposition for 35min to obtain the D/CFS.
(5) Washing the D/CFS with deionized water, drying, and roasting the sample in a tubular furnace at 350 ℃ for 5h in the air atmosphere to obtain MnO2-RuO2a/CFS composite electrode. (recorded as electrode # 3).
RuO prepared as in examples 2-5, respectively2the/CFS composite electrode and the No. 1-3 electrode are used as anodes, pure carbon fiber cloth with the same size is used as a cathode to form an electrolysis device, the voltage is applied to 1.5V, the current is 0.15A, a certain electrolyte NaCl is added into an aqueous solution containing methylene blue, the concentration of the electrolyte NaCl is 15g/L, the electrifying electrolysis time is 30min, and the test results are shown in Table 2.
Table 2:
as can be seen from Table 2, different MnO ranges given in the present invention were made2Effect of doping amount on methylene blue removal and COD removal in comparison with RuO prepared in example 22/CFS (undoped) and 1# MnO2-RuO2[ 2# MnO prepared in example 4 ] CFS (doping amount 0.01mol/L) ]2-RuO2/CFS electrode and 3# MnO prepared in example 52-RuO2the/CFS electrode obviously improves the methylene blue removal rate and the COD removal rate, which indicates MnO2With RuO2Synergistic, relative to the active metal RuO of a single component2And the methylene blue removal rate and the COD removal rate can be obviously improved. From the economic benefit analysis, the optimum doping amount is about 0.9895g (0.05mol/L), and MnO in the final electrode2Account forPreferably 45-65 wt.% of the active metal oxide.
Example 7
The performance of the electrode material is tested by adopting an Autolab type electrochemical workstation of Wantong Switzerland, and a three-electrode system is adopted for testing. The three electrodes prepared in examples 1 to 3 were used as working electrodes, a Pt sheet electrode as a counter electrode, and Ag/AgCl as a reference electrode. 5mol/LNaCl solution is selected as electrolyte, Cyclic Voltammetry (CV) test is carried out at room temperature, and the scanning rate is 20 mV.S-1The results are shown in FIG. 8 for the scan voltages of-1 to 1V.
As can be seen, the RuO prepared in example 22/CFS and MnO prepared in example 32-RuO2CFS, where both electrodes show oxidation peaks in the same location, but MnO as prepared in example 32-RuO2the/CFS electrode peak height is higher, the current density is stronger, and the electrocatalytic activity is better.
Comparative example 2
This comparative example employed a co-electrochemical deposition process to deposit MnO on the CFS surface simultaneously2And RuO2Preparation of MnO2-RuO2the/CFS composite electrode comprises the following steps:
(1) cutting off 2 x 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous ethanol and ultrapure water for 35min, respectively, removing soluble impurities, cleaning with deionized water for multiple times, and naturally drying at room temperature to obtain A/CFS.
(2) The A/CFS was placed in 50ml of mixed acid (concentrated H)2SO4With HNO3According to the volume ratio of 1: 1) in the water solution, heating and boiling for 1 hour by an electric furnace, taking out the carbon cloth for cooling, washing the carbon cloth by a large amount of deionized water until no acidity exists, and then carrying out forced air drying for 6 hours at 120 ℃ in a forced air drying box to obtain B/CFS.
(3) 0.1970g (0.01mol) of MnCl are taken2·4H2O、0.1307g RuCl3·3H2O is dissolved in 200ml of deionized water, 102.5ul of concentrated hydrochloric acid and 1.873g of KCl are added, and the mixture is uniformly mixed and stirred to obtain a uniformly mixed solution C.
(4) 80ml of solution C is taken as the electrodeposition solution in an electrolytic bath, B/CFS is taken as the cathode, and the current density is set to be 25 mA-cm2And electrifying to deposit for 65min to obtain D/CFS.
(5) Washing the D/CFS with deionized water, drying, and roasting the sample in a tubular furnace at 350 ℃ for 5h in the air atmosphere to obtain MnO2-RuO2the/CFS composite electrode (denoted as # 4 electrode).
The 1# composite electrode prepared in example 3 and the 4# composite electrode prepared in comparative example 2 were used as anodes, carbon fiber cloths of the same size were used as cathodes to form an electrolysis apparatus, methylene blue wastewater was electrolytically treated at a voltage of 1.5V and a current of 0.15A, NaCl was added to give a NaCl concentration of 15g/L in the wastewater, and the energization electrolysis time was 30 min. The methylene blue removal effect is shown in table 3:
TABLE 3
| Composite electrode | Methylene blue removal rate/%) | COD removal rate/%) |
| 1# electrode | 98.35％ | 76.98％ |
| 4# electrode | 72.33％ | 58.11％ |
As can be seen from the table, 1# MnO prepared in example 32-RuO2The removal rate of methylene blue in the wastewater by the/CFS composite electrode is 98.35 percent, and the removal rate of COD is 76.98 percent; and 4# MnO prepared in comparative example 22-RuO2Removal of methylene blue by/CFS composite electrodeThe removal rate is only 72.33%, and the COD removal rate is only 58.11%. Therefore, the composite electrode prepared by the step electrodeposition method is superior to the synchronous electrodeposition method. This phenomenon is mainly due to Ru during electrodeposition3+And Mn2+During the reduction reaction of the cathode, there is an ion competition effect, Ru3+The electron obtaining capability of the alloy is superior to that of Mn2+And the metal Ru is firstly deposited on the cathode CFS, and then the Ru is covered with Mn, the coating section on the surface of the composite electrode CFS is mainly a sandwich coating, and compared with the step-by-step electrodeposition, the generated electrodeposition layer is uneven and has poor compactness. Composite electrode obtained by roasting in an aerobic atmosphere, RuO thereof2Can not be repeated with Cl in organic wastewater-Contact, not to exert RuO effectively2This phase and MnO thereof2Synergistic catalytic chlorine evolution performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the composite electrode for treating the high-chlorine organic wastewater is characterized by comprising the following steps of:
s1, pretreatment of the carbon fiber cloth: after the carbon fiber cloth is decontaminated, deoiled and cleaned, acid oxidation is carried out, and oxygen-containing hydrophilic groups are formed on the surface of the carbon fiber cloth, so that the carbon fiber cloth has hydrophilicity;
s2, first-step electrodeposition: respectively taking the carbon fiber cloth prepared in the step S1 as an anode and a cathode, taking an aqueous solution of ruthenium salt as electrodeposition liquid, and carrying out electrodeposition to obtain a Ru/CFS electrode on the cathode side;
s3, first-step roasting: the Ru/CFS electrode is washed by deionized water, dried and roasted at the temperature of 150-350 ℃ in oxygen-containing atmosphere to obtain RuO2/CAn FS electrode;
s4, second-step electrodeposition: the carbon fiber cloth prepared in step S1 is used as an anode, RuO is used2Taking a/CFS electrode as a cathode, taking an aqueous solution of manganese salt as an electrodeposition solution, electrifying electrodeposition to obtain Mn-RuO on the cathode side2a/CFS electrode;
s5, second-step roasting: adding Mn-RuO2the/CFS electrode is washed and dried by deionized water and is roasted at the temperature of 150 ℃ and 350 ℃ in oxygen-containing atmosphere to obtain MnO for treating high-chlorine organic wastewater2-RuO2a/CFS composite electrode.
2. The method according to claim 1, wherein the S1 method comprises: ultrasonically cleaning carbon fiber cloth by using deionized water, absolute ethyl alcohol and acetone, placing the carbon fiber cloth into mixed concentrated acid of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:1, heating for 1-2h, and drying for later use.
3. The method of claim 1, wherein the S2 bath is prepared by the following steps: dissolving soluble ruthenium salt or hydrate thereof, concentrated hydrochloric acid and KCl/sodium chloride in deionized water, and uniformly mixing and stirring to obtain electrodeposition liquid; the soluble ruthenium salt is RuCl3、Ru(NO)3Or Ru2(SO4)3。
4. The method of claim 3 wherein the concentration of each ion in the electrodeposition bath of S2 is Ru3+:0.05～0.06mol/L，Cl-:0.01～0.025mol/L，K+:0.010～0.015mol/L。
5. The method of claim 1, wherein the bath in S4 is prepared by: dissolving soluble manganese salt or hydrate thereof, concentrated hydrochloric acid and KCl/sodium chloride in deionized water, and uniformly mixing and stirring to obtain electrodeposition liquid; wherein the soluble manganese salt is manganese nitrate or manganese chloride.
6. The method according to claim 5, wherein the electrodeposition in S4The concentration of each ion in the solution is Mn2+:0.1～0.2mol/L，Cl-:0.015～0.030mol/L，K+:0.010～0.015mol/L。
7. The method according to claim 1, wherein the electrodeposition reaction is carried out in S2 at a current density of 20 to 25 mA-cm-2The electrodeposition time is 35 min-1 h.
8. The method according to claim 1, wherein the firing in S3 or S5 is carried out in an air atmosphere, and the temperature rising rate at the time of firing is 60 to 70 ℃/h.
9. A method for treating high-chlorine organic wastewater, which is characterized in that an electrolysis device consisting of a composite electrode prepared by the preparation method of any one of claims 1 to 8 as an anode and carbon fiber cloth with the same size as the anode is used for electrolyzing the organic wastewater, wherein the current is 0.15V-3V, and the electrifying time is 0.5-3 h.
10. The method according to claim 9, wherein NaCl is added to the organic waste water before the electrolysis to achieve a NaCl concentration in the organic waste water of 25 to 40 g/L.
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