CN113562812B - 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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- 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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- 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 decontamination, deoiling and cleaning are carried out on carbon fiber cloth, 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: washing Ru/CFS electrode with water, drying, and calcining at 150-350 deg.C in oxygen-containing atmosphere to obtain RuO 2 a/CFS electrode; s4, electrodeposition: carbon fiber cloth is used as an anode, and RuO is used 2 Taking 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 side 2 a/CFS electrode; s5, roasting: adding Mn-RuO 2 /CFS electrode is washed by water, dried and roasted at 150-350 ℃ in oxygen-containing atmosphere to obtain MnO for treating high-chlorine organic wastewater 2 ‑RuO 2 a/CFS composite electrode. The invention solves the problems of easy generation of cracks on the surface of the electrode, easy passivation of the electrode, low treatment efficiency of chloride ions 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 treat high-chlorine organic wastewater efficiently and cleanly 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 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 150-350 ℃ in oxygen-containing atmosphere to obtain RuO 2 a/CFS electrode;
s4, second-step electrodeposition: taking the carbon fiber cloth prepared in the step S1 as an anode and RuO 2 Taking 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 side 2 a/CFS electrode;
s5, second-step roasting: adding Mn-RuO 2 the/CFS electrode is washed by deionized water, dried and roasted at 150-350 ℃ in oxygen-containing atmosphere to obtain MnO for treating high-chlorine organic wastewater 2 -RuO 2 a/CFS composite electrode.
According to a preferred embodiment of the present invention, 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 1:1 in volume ratio, heating for 1-2h, and drying for later use.
Wherein, the drying conditions are as follows: drying with air blast at 105-120 deg.C for 5-8 hr.
According to a 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 RuCl 3 、Ru(NO) 3 Or Ru 2 (SO 4 ) 3 。
According to a preferred embodiment of the present invention, the concentration of each ion in the electrodeposition bath in S2 is: ru 3+ :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 an electrodeposition solution; wherein the soluble manganese salt is manganese nitrate or manganese chloride.
According to a preferred embodiment of the present invention, the concentration of each ion in the electrodeposition bath in S4 is:
Mn 2+ :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 at the time of electrodeposition reaction in S2 is 20 to 25mA cm -2 The electrodeposition time is 35 min-1 h.
As mentioned above, 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 accumulation density of metal atoms on the CFS from being affected by too small conductivity, high energy consumption and too slow reaction speed of the electrodeposition liquid; 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 a preferred embodiment of the present invention, the drying conditions of S3 and S5 are: drying by blowing at 50-65 deg.C for 6-8 hr.
According to a preferred embodiment of the present invention, the baking in S3 and S5 is performed in an air atmosphere, and the temperature rise 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 the composite electrode prepared in any one of the above embodiments as an anode and the carbon fiber cloth with the same size as the cathode is used for electrolyzing the organic wastewater, the current is 0.15V-3V, and the electrifying time is 0.5-3h.
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 40g/L. Preferably, the organic wastewater is an organic wastewater containing methylene blue. Preferably, the concentration of methylene blue in the organic wastewater is 40-60mg/L, and the COD of the organic wastewater is 100-200mg/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 invention 2 -RuO 2 the/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 RuO 2 And MnO 2 The carbon fiber cloth is a braided fabric obtained by weaving carbon fibers, the surface of the carbon fiber cloth is three-dimensional grains, and the three-dimensional grains 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 remarkably improved, the number of active sites on the surface of the composite electrode is greatly increased, and 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 load RuO in sequence 2 And MnO 2 The 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 surface 2 And MnO 2 The 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. RuO 2 And MnO 2 Can form solid solution between the electrode and the anode, prevent the corrosion of corrosive acid and alkali or electrolyte, effectively prevent the diffusion of oxidizing substances and corrosive electrolyte, ensure that the electrode has longer service life and can also improve the chlorine evolution efficiency.
(3) The invention uses CFS as a substrate and adopts an electrodeposition method to load RuO firstly 2 Reloading MnO 2 MnO prepared by the step-by-step loading method 2 -RuO 2 Compared 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 occur 2 Passivation 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 3 2 、MnO 2 Standard card contrast)
FIGS. 2 and 3 are scanning electron micrographs of the pretreated pure carbon fiber cloth of example 1 at different magnification.
FIGS. 4 and 5 show RuO as an electrode sample obtained in example 2 2 Scanning electron microscopy of/CFS.
FIGS. 6 and 7 show MnO as electrode samples obtained in example 3 2 -RuO 2 Scanning 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) 2 SO 4 With HNO 3 According 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 RuO 2 the/CFS composite electrode comprises the following steps:
(1) Cutting off 2X 2cm carbon fiber cloth, ultrasonic cleaning in acetone, anhydrous alcohol and ultrapure water for 35min, respectively, washing off soluble impurities, washing 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) 2 SO 4 With HNO 3 According to the volume ratio of 1: 1) in the 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) Weighing 0.1307g RuCl 3 ·3H 2 O is dissolved in 100ml of deionized water, and 12.5ul of concentrated hydrochloric acid and 1.1238g KCl are added, mixed evenly and stirred to obtain a mixed even 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/cm 2 And electrifying for electrodeposition for 35min to obtain the D/CFS.
(5) D/CFS is washed by deionized water, dried and then the sample is placedRoasting for 5 hours at 350 ℃ in the air atmosphere of a tube furnace to obtain the RuO 2 a/CFS electrode.
Comparative example 1
This comparative example uses an activated carbon plate as a substrate to prepare RuO 2 The 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 gGluCl 3 ·3H 2 O is dissolved in 100ml of deionized water, and 12.5ul of concentrated hydrochloric acid and 1.1238g of KCl are added, mixed uniformly and stirred to obtain a uniformly mixed solution B.
(3) Taking 40ml of solution B and an electrolytic tank as an electrodeposition solution, taking a pretreated electrode A as a cathode, and setting the current density at 25mA/cm 2 And electrifying to deposit for 35min to obtain the 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 RuO 2 And (3) compounding an active carbon electrode.
Respectively with RuO of comparative example 1 2 Composite activated carbon electrode, pure carbon fiber cloth of example 1 and RuO of example 2 2 the/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, the electrifying electrolysis time is 30min, and the 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 | RuO 2 /CFS | 86.23％ | 60.52％ |
| Comparative example 1 | RuO 2 Composite active carbon electrode | 62.82％ | 48.42％ |
As can be seen from Table 1, the RuO produced in example 2 2 The removal rate of the/CFS electrode to methylene blue and COD is higher than that of the traditional RuO 2 The composite active carbon electrode and the unmodified pure carbon fiber cloth electrode in the market are greatly improved. The reason is that the three-dimensional reticular carbon fiber cloth is used as a matrix material, and compared with the traditional activated carbon material, the three-dimensional reticular carbon fiber cloth can increase the attachment area of the active sites and improve the electrocatalytic reaction rate. 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 example 2 -RuO 2 the/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) 2 SO 4 With HNO 3 According 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 (0.01 mol) of MnCl is taken 2 ·4H 2 Dissolving O in 100ml deionized water, adding 89.9ul concentrated hydrochloric acid and 0.7492g KCl, uniformly mixing and stirring to obtain a uniformly mixed solution C.
(4) 40ml of solution C was taken as an electrodeposition solution in an electrolytic bath with RuO prepared according to the method of example 2 2 the/CFS electrode was used as cathode and the current density was set at 25mA/cm 2 And 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 MnO 2 -RuO 2 the/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 diffractometer 2 /CFS electrode and MnO prepared in example 3 2 -RuO 2 Component structure of/CFS electrode coating. As shown in fig. 1. Wherein, mnO prepared in example 3 2 -RuO 2 The X-ray diffraction intensity of the/CFS electrode coating is maximum, and MnO can be detected 2 And RuO 2 A two-phase metal oxide; thus, mnO has been explained 2 And RuO 2 The 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 RuO 2 The standard XRD spectrum can confirm that Ru is RuO 2 Active component of CFS electrode.
The pure carbon fiber cloth of example 1 and RuO prepared in example 2 were observed by a scanning electron microscope 2 /CFS electrode and MnO prepared in example 3 2 -RuO 2 Surface morphology of/CFS electrode。
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 has three-dimensional lines, wherein the three-dimensional lines comprise special structures such as a slender cylindrical fiber surface, fine gaps among the 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 2 2 Scanning electron microscopy of/CFS. As shown in FIGS. 6 and 7, mnO was added to the electrode sample obtained in example 3 2 -RuO 2 Scanning electron micrograph of/CFS. As can be seen in connection with FIGS. 4-7, ruO 2 MnO distributed on the CFS surface in fine velvet-like dispersion interval 2 Then embedded in RuO in granular form 2 In the gap of (1), overall presents RuO 2 Particles and MnO 2 The particles are embedded with each other, and the surface of the carbon fiber cloth is uniformly loaded with spherical MnO 2 After 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 MnO 2 -RuO 2 a/CFS electrode.
Example 4
Preparation of MnO in this example 2 -RuO 2 The method comprises the following steps of:
(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) 2 SO 4 With HNO 3 According to the volume ratio of 1:1, heating in an electric furnace to boil for 1 hour, taking out the carbon cloth, cooling, washing with a large amount of deionized water until no acidity exists, and performing forced air drying at 120 ℃ for 6 hours in a forced air drying oven to obtain B/CFS.
(3) 0.9895g (0.05 mol) of MnCl is taken 2 ·4H 2 Dissolving O in 100ml deionized water, adding 89.9ul concentrated hydrochloric acid and 0.7492g KCl, uniformly mixing and stirring 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 2 2 the/CFS electrode was used as cathode and the current density was set at 25mA/cm 2 And 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 5 hours in the air atmosphere to obtain MnO 2 -RuO 2 the/CFS composite electrode (recorded as electrode # 2).
Example 5
Preparation of MnO in this example 2 -RuO 2 the/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) 2 SO 4 With HNO 3 According 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 (0.10 mol) of MnCl is taken 2 Dissolving 4H2O in 100ml of deionized water, adding 89.9ul of concentrated hydrochloric acid and 0.7492g of KCl, and uniformly mixing and stirring to obtain a uniformly mixed solution C.
(4) 40ml of solution C was taken as an electrodeposition solution in an electrolytic bath with RuO prepared according to the method of example 2 2 the/CFS electrode was used as cathode and the current density was set at 25mA/cm 2 And 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 MnO 2 -RuO 2 a/CFS composite electrode. (recorded as electrode # 3).
Prepared by the following steps of examples 2 to 5 respectivelyPrepared RuO 2 the/CFS composite electrode and the 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 =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 made 2 Effect of doping amount on methylene blue removal and COD removal in comparison with RuO prepared in example 2 2 /CFS (undoped) and 1# MnO 2 -RuO 2 PerCFS (doping 0.01 mol/L), 2# MnO prepared in example 4 2 -RuO 2 /CFS electrode and 3# MnO prepared in example 5 2 -RuO 2 the/CFS electrode obviously improves the methylene blue removal rate and the COD removal rate, which indicates MnO 2 And RuO 2 Synergistic, relative to the active metal RuO of a single component 2 And the methylene blue removal rate and the COD removal rate can be obviously improved. From the economic benefit analysis, the optimum doping amount is 0.9895g (0.05 mol/L), and MnO in the final electrode 2 Preferably 45-65wt.% of the total 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 -1 The scanning voltages were-1 to 1V, and the results are shown in FIG. 8.
From the figures, it can be seen thatRuO prepared in example 2 2 /CFS and MnO prepared in example 3 2 -RuO 2 CFS, both electrodes showed the same oxidation peak, but MnO was prepared as in example 3 2 -RuO 2 the/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 simultaneously 2 And RuO 2 Preparation of MnO 2 -RuO 2 the/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) 2 SO 4 With HNO 3 According to the volume ratio of 1:1, heating in an electric furnace to boil for 1 hour, taking out the carbon cloth, cooling, washing with a large amount of deionized water until no acidity exists, and performing forced air drying at 120 ℃ for 6 hours in a forced air drying oven to obtain B/CFS.
(3) 0.1970g (0.01 mol) of MnCl is taken 2 ·4H 2 O、0.1307g RuCl 3 ·3H 2 O 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 an electro-deposition solution in an electrolytic bath, B/CFS is taken as a cathode, and the current density is set to be 25mA/cm 2 And electrifying for electrodeposition for 65min 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 5 hours in the air atmosphere to obtain MnO 2 -RuO 2 the/CFS composite electrode (designated as the # 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 30min. 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 3 2 -RuO 2 The 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 2 2 -RuO 2 The removal rate of the/CFS composite electrode to methylene blue is only 72.33%, and the removal rate of COD 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 electrodeposition 3+ And Mn 2+ During the reduction reaction of the cathode, there is an ion competition effect, ru 3+ The electron obtaining capability of the alloy is superior to that of Mn 2+ 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. Obtained by roasting in an aerobic atmosphereComposite electrode of RuO 2 Can not be repeated with Cl in organic wastewater - Contact, not to exert RuO effectively 2 This phase and MnO thereof 2 Synergistic 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 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 an electrodeposition solution, and performing 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 150-350 ℃ in oxygen-containing atmosphere to obtain RuO 2 a/CFS electrode;
s4, second-step electrodeposition: taking the carbon fiber cloth prepared in the step S1 as an anode and RuO 2 Taking 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 side 2 a/CFS electrode;
s5, second-step roasting: adding Mn-RuO 2 The CFS electrode is washed by deionized water, dried and roasted at 150-350 ℃ in oxygen-containing atmosphere to obtain MnO for treating high-chlorine organic wastewater 2 -RuO 2 a/CFS composite electrode.
2. The method according to claim 1, wherein the S1 process is: ultrasonically cleaning the carbon fiber cloth by using deionized water, absolute ethyl alcohol and acetone, placing the carbon fiber cloth into mixed concentrated acid with the volume ratio of concentrated sulfuric acid to concentrated nitric acid 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 an electrodeposition solution; the soluble ruthenium salt is RuCl 3 、Ru(NO) 3 Or Ru 2 (SO 4 ) 3 。
4. The method of claim 3, wherein the concentration of each ion in the electrodeposition bath in S2 is Ru 3+ :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 an electrodeposition solution; wherein the soluble manganese salt is manganese nitrate or manganese chloride.
6. The method of claim 5, wherein the electrodeposition bath in S4 has a concentration of each ion of Mn 2+ :0.1～0.2mol/L，Cl - :0.015～0.030mol/L，K + :0.010～0.015mol/L。
7. The production method according to claim 1, wherein the electrodeposition reaction is carried out in S2 at a current density of 20 to 25 mA-cm -2 The electrodeposition time is 35 min-1 h.
8. The method according to claim 1, wherein the firing in S3 and S5 is carried out in an air atmosphere, and the temperature rise rate at the time of firing is 60 to 70 ℃/h.
9. A method for treating high-chlorine organic wastewater, 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, the current is 0.15V-3V, and the electrifying time is 0.5-3h.
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 40g/L.
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