CN111484104A - Electrode for electrochemically degrading aniline, and electrode manufacturing method and device - Google Patents
Electrode for electrochemically degrading aniline, and electrode manufacturing method and device Download PDFInfo
- Publication number
- CN111484104A CN111484104A CN202010252339.6A CN202010252339A CN111484104A CN 111484104 A CN111484104 A CN 111484104A CN 202010252339 A CN202010252339 A CN 202010252339A CN 111484104 A CN111484104 A CN 111484104A
- Authority
- CN
- China
- Prior art keywords
- electrode
- titanium
- titanium dioxide
- time
- dioxide nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
A method of making an electrode for electrochemical degradation of aniline, comprising: (1) pretreating a titanium substrate; (2) taking the pretreated titanium substrate as an anode and graphite as a cathode, and carrying out anodic oxidation reaction in electrolyte to form regularly arranged titanium dioxide nano array tubes on the titanium substrate; (3) doping iron ions into the titanium dioxide nano array tube to obtain a titanium substrate covered by the iron-doped titanium dioxide nano array tube; (4) performing electrochemical deposition by taking a titanium substrate covered by the iron-doped titanium dioxide nano array tube as a cathode, a graphite electrode as an anode and a tin-antimony solution as a deposition solution; (5) and calcining the titanium substrate covered by the iron-doped titanium dioxide nano array tube deposited with tin and antimony at a set temperature to obtain the electrode with the structure of antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate. An electrode and a device for electrochemically degrading aniline are also disclosed.
Description
Technical Field
The application belongs to the technical field of electrochemistry, and particularly relates to an electrode for electrochemically degrading aniline, and a manufacturing method and a manufacturing device of the electrode.
Background
Aniline is an important industrial raw material and widely applied to industries such as medicine, agriculture, dye, military industry and the like, but aniline is a substance which seriously pollutes the environment and harms human health. Therefore, the aniline wastewater is discharged into the environment without being treated, which will have serious consequences. In recent years, researchers have found many methods for treating organic matters in wastewater, such as biodegradation, membrane filtration, and chemical oxidation, but these methods have low degradation efficiency, small application range, easy generation of secondary pollution, and high price, and thus are difficult to be widely used.
In recent years, electrochemical oxidation has attracted much attention due to its high efficiency, low cost, and environmental friendliness. The anode electrode material is a key factor determining the effect of the electrochemical oxidation method, so that the development of a high-efficiency anode electrode material is particularly important. Currently, a variety of electrode materials have been explored. The BBD electrode has good stability and high oxygen evolution potential, but the BBD electrode is expensive and difficult to be widely applied. RuO2、IrO2The electrode has lower oxygen evolution potential, thereby reducing the efficiency of decomposing organic matters and being difficult to be widely applied. PbO2Good stability of electrode, high catalytic activity, but easy to separate out toxic Pb2+Preventing the wide application of the electrode. SnO2Has the advantages of high oxygen evolution potential, low price, easy obtainment, environmental protection and the like, and is expected to be widely applied to the treatment of organic wastewater.
However, SnO2The electrodes also have many disadvantages, such as low stability, short life, poor conductivity, etc. Ti/TiO modified by highly ordered titanium dioxide nano array tube2-NTs/SnO2the-Sb electrode has higher oxygen evolution potential (more than 2.1V), longer service life and higher catalytic activity. Thus, passing through highly ordered titanium dioxide nanoarray Tubes (TiO)2NTs) modified titanium-based tin antimony electrode is a high-efficiency anode with wide application prospect. However, since titanium dioxide is a semiconductor, the charge transfer resistance is large, and the electrode is loweredThe current utilization efficiency and the catalytic efficiency hinder the wide application of the electrode.
Disclosure of Invention
In order to solve at least one of the above-mentioned technical problems of the prior art, in one aspect, an embodiment of the present application discloses a method for manufacturing an electrode for electrochemically degrading aniline, the method comprising:
(1) pretreating a titanium substrate;
(2) taking the pretreated titanium substrate as an anode and graphite as a cathode, and carrying out anodic oxidation reaction in electrolyte to form regularly arranged titanium dioxide nano array tubes on the titanium substrate;
(3) doping iron ions into the titanium dioxide nano array tube to obtain a titanium substrate covered by the iron-doped titanium dioxide nano array tube;
(4) taking a titanium substrate covered by the iron-doped titanium dioxide nano array tube as a cathode, a graphite electrode as an anode and a tin-antimony solution as a deposition solution, and carrying out electrochemical deposition;
(5) and calcining the titanium substrate covered by the iron-doped titanium dioxide nano array tube deposited with tin and antimony at a set temperature to obtain the electrode with the structure of antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate.
Further, some embodiments disclose a method for manufacturing an electrode for electrochemically degrading aniline, the pre-treating a titanium substrate comprising:
(1-1) grinding a titanium substrate;
(1-2) cleaning the polished titanium substrate;
(1-3) etching the cleaned titanium substrate in an etching solution, wherein the etching solution is a mixed solution of nitric acid and hydrofluoric acid, the concentration of the nitric acid is 27.43 g/L, and the concentration of the hydrofluoric acid is 83.84 g/L.
In some embodiments, the voltage of the anodic oxidation reaction is set to be 20-25V, the reaction time is set to be 20-90 min, and the electrolyte comprises, by mass, 9-20 parts of HF, 350 parts of ethylene glycol and 650 parts of deionized water.
Some embodiments disclose a method for manufacturing an electrode for electrochemically degrading aniline, wherein doping iron ions into titanium dioxide nanotubes comprises:
(3-1) placing the titanium substrate covered by the titanium dioxide nano array tube in Fe3+Dipping in the solution for a set time;
(3-2) washing and drying the titanium substrate covered by the dipped titanium dioxide nano array tube;
and (3-3) calcining the titanium substrate covered by the dried titanium dioxide nano array tube at 350-500 ℃ for a set time.
Further, some embodiments disclose methods for manufacturing an electrode for electrochemically degrading aniline, in which a titanium substrate covered with a titanium dioxide nano-array tube is FeCl3The time for dipping in the solution is set to be 3-10 min, and the calcination time of the titanium substrate covered by the dried titanium dioxide nano array tube is set to be 1-2 h.
Some embodiments disclose methods of making an electrode for electrochemical degradation of aniline, the electrochemical deposition comprising:
(4-1) first pulse electrodeposition wherein the on time of the first positive pulse is set to 10 to 100ms, the off time is set to 89 to 589ms, and the pulse current is set to 30 to 100 mA-cm-2(ii) a The on time of the first negative pulse is set to be 1-10 ms, the off time is set to be 0, and the pulse current is set to be 3-10 mA-cm-2；
(4-2) second pulse electrodeposition, wherein the on time of the second positive pulse is set to 0.2 to 0.8ms, the off time is set to 0.8 to 0.2ms, and the pulse current is set to 10 to 50 mA-cm-2(ii) a The on time of the first negative pulse is set to be 0.1-0.9 ms, the off time is set to be 0.9-0.1 ms, and the pulse current is set to be 1-5 mA-cm-2。
Further, in some embodiments of the method for manufacturing an electrode for electrochemically degrading aniline, the time for the first pulse electrodeposition is set to be 15-40 min, and the time for the second pulse electrodeposition is set to be 45-120 min.
Some embodiments disclose a method for manufacturing an electrode for electrochemically degrading aniline, the deposition solution includes:
on the other hand, some embodiments disclose an electrode for electrochemically degrading aniline, which is obtained by the method for manufacturing an electrode for electrochemically degrading aniline disclosed in the embodiments of the present application, and the electrode specifically includes:
a titanium substrate;
a layer of titanium dioxide nano array tube is covered on the titanium substrate, wherein iron ions are doped in the titanium dioxide nano array tube;
a layer of tin dioxide doped with antimony is deposited on the outer side of the titanium dioxide nano-array tube.
In one aspect, some embodiments disclosed herein disclose a device for electrochemically degrading aniline, the device comprising an electrode for electrochemically degrading aniline as disclosed herein.
The method for manufacturing the electrode for electrochemically degrading the aniline, disclosed by the embodiment of the application, is characterized in that metal titanium is used as a substrate, iron ions are doped in a titanium dioxide nano array tube, and an antimony-doped tin dioxide catalyst is formed through two pulse electrodeposition, so that the electrode with an antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate structure is obtained, the charge transfer resistance of the traditional titanium dioxide nano array tube electrode is effectively reduced, the oxygen evolution potential of the electrode is improved, the electrode is used for the electrochemical degradation process of the aniline, the electrode structure is stable, the catalytic activity is high, the degradation efficiency is high, the service life is long, and the electrode can also be used for other molecular electrochemical degradation processes with benzene ring structures.
Detailed Description
The word "embodiment" as used herein, is not necessarily to be construed as preferred or advantageous over other embodiments, including any embodiment illustrated as "exemplary". Performance index tests in the examples of this application, unless otherwise indicated, were performed using routine experimentation in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly employed by those of ordinary skill in the art.
As used herein, the terms "substantially" and "about" are used to describe small fluctuations, e.g., they may refer to less than or equal to + -5%, such as less than or equal to + -2%, such as less than or equal to + -1%, such as less than or equal to + -0.5%, such as less than or equal to + -0.2%, such as less than or equal to + -0.1%, such as less than or equal to + -0.05%, concentrations, amounts, and other numerical data may be expressed or presented herein in a range format, such range format being used for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or subranges encompassed within the range, e.g., "1 to 5" and to include not only the explicitly recited values from 1% to 5%, but also individual values and subranges within the indicated range, and thus, including individual values within such range, such as 2%, 3.5% and subranges, such as 1% to 3%, and such ranges, such as 1% to 3% and 5% and such ranges, unless otherwise stated, such a matter is commonly referred to a molar concentration, such as a molar or a molar ratio, such as a molar ratio, or a molar ratio, and a range, unless otherwise indicated to indicate that a range, such a range, and a range, such a range, would be included in a range, would be included, and a range, unless a range, would be included.
In this disclosure, including the claims, all conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are to be understood as being open-ended, i.e., to mean" including but not limited to. Only the conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, apparatuses, etc. known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application. On the premise of no conflict, the technical features disclosed in the embodiments of the present application may be combined arbitrarily, and the obtained technical solution belongs to the content disclosed in the embodiments of the present application.
In some embodiments, a method of making an electrode for electrochemical degradation of aniline comprises:
(1) pretreating a titanium substrate;
(2) taking the pretreated titanium substrate as an anode and graphite as a cathode, and carrying out anodic oxidation reaction in electrolyte to form regularly arranged titanium dioxide nano array tubes on the titanium substrate;
(3) doping iron ions into the titanium dioxide nano array tube to obtain a titanium substrate covered by the iron-doped titanium dioxide nano array tube;
(4) taking a titanium substrate covered by the iron-doped titanium dioxide nano array tube as a cathode, a graphite electrode as an anode and a tin-antimony solution as a deposition solution, and carrying out electrochemical deposition;
(5) and calcining the titanium substrate covered by the iron-doped titanium dioxide nano array tube deposited with tin and antimony at a set temperature to obtain the electrode with the structure of antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate.
As an alternative embodiment, the pre-treating the titanium substrate comprises:
(1-1) grinding a titanium substrate; the titanium plate is usually selected as a titanium substrate, and is ground by using sand paper with a suitable mesh number so as to obtain a smooth surface of the titanium plate and remove impurities. For example, a titanium plate may be ground with 600 mesh and 1200 mesh sandpaper in sequence. As an alternative embodiment, a titanium rod, a titanium sheet, or the like may also be selected as the titanium substrate.
(1-2) cleaning the polished titanium substrate; the polished titanium substrate is usually cleaned to remove impurity molecules on the surface of the titanium substrate. For example, the polished titanium plate may be ultrasonically cleaned with absolute ethanol, and then washed with deionized water to completely remove impurity molecules.
(1-3) etching the cleaned titanium substrate in an etching solution, wherein the etching solution is a mixed solution of nitric acid and hydrofluoric acid, the concentration of the nitric acid is 27.43 g/L, and the concentration of the hydrofluoric acid is 83.84 g/L.
In some embodiments, the voltage of the anodic oxidation reaction is set to be 20-25V, the reaction time is set to be 20-90 min, and the electrolyte comprises, by mass, 9-20 parts of HF, 350 parts of ethylene glycol and 650 parts of deionized water. The voltage of the anodic oxidation reaction has important influence on the form of the product, for example, the diameter of the titanium dioxide nanotube can be directly influenced by the voltage, and the control of the diameter of the titanium dioxide nanotube is favorable for controlling the form and the service performance and prolonging the service life of the titanium dioxide nanotube on one hand, and can be favorable for the doping of iron ions in the subsequent process on the other hand; the reaction time directly influences the length of the titanium dioxide nanotube, and the proper length is beneficial to controlling the form and the service performance of the titanium dioxide nanotube and prolonging the service life, so that the titanium dioxide nanotube which meets the requirement can be obtained only by selecting proper voltage and reaction time; for example, the voltage can be selected from 20V, 21V, 22V, 23V, 24V, 25V and the like, and can be any value between 20V and 25V; the reaction time can be any value within the range of 20-90 min such as 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min and the like.
Some embodiments disclose a method for manufacturing an electrode for electrochemically degrading aniline, wherein doping iron ions into titanium dioxide nanotubes comprises:
(3-1) placing the titanium substrate covered by the titanium dioxide nano array tube in Fe3+The solution was immersed for a predetermined time. The titanium plate after anodic oxidation is usually required to be washed to remove impurity ions left on the titanium plate, and for example, the titanium plate can be sequentially washed in absolute ethyl alcohol and deionized water; after cleaning, the titanium substrate is soaked in a solution containing iron ions, and the iron ions are doped in the titanium dioxide nano array tube formed on the surface of the titanium substrate, wherein the ferric ion solution is an inorganic salt solution containing ferric ions in the solution, such as FeCl3、Fe(NO3)3、Fe2(SO4)3And the like.
And (3-2) washing and drying the titanium substrate covered by the dipped titanium dioxide nano array tube. After the dipping is finished, the titanium substrate covered by the titanium dioxide nano array tube doped with iron ions is usually washed and dried; for example, the film may be dried in a clean air atmosphere at room temperature after being washed with deionized water several times.
(3-3) calcining the titanium substrate covered by the dried titanium dioxide nano array tube at 350-500 ℃ for a set time; generally, the microstructure of the titanium dioxide nano array tube generated by anodic oxidation reaction is in an amorphous state, the conductivity and the mechanical property of the titanium dioxide nano array tube are poor, the microstructure of the titanium dioxide nano array tube can be converted into regular anatase type titanium dioxide by calcining heat treatment at a proper temperature, and the guiding property and the mechanical property of the titanium dioxide nano array tube can be greatly improved; the calcination is usually carried out in a high temperature furnace, for example, sintering may be carried out in a muffle furnace, and the heating temperature of the muffle furnace may be set to 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or the like.
As an alternative embodiment, the solution containing iron ions is selected from FeCl3The concentration of the solution is set between 0.5 mol/L and 1.5 mol/L so as to control the doping efficiency and doping amount of iron ions, for example, 0.5 mol/L, 0.6 mol/L0, 0.7 mol/L1, 0.8 mol/L, 0.9 mol/L, 1.0 mol/L, 1.1 mol/L, 1.2 mol/L, 1.3 mol/L, 1.4 mol/L, 1.5 mol/L and the like can be selected.
As an alternative embodiment, the titanium substrate covered by the titanium dioxide nano array tube is FeCl3The time for dipping in the solution is set to be 3-10 min so as to obtain the appropriate iron ion doping amount. For example, the dipping time may be selected from 3min,4min、5min、6min、7min、8min、9min、10min。
As an optional embodiment, the calcination time of the titanium substrate covered by the dried titanium dioxide nano array tube is set to be 1-2 h.
As an alternative embodiment, in the method for manufacturing an electrode for electrochemical degradation of aniline, the electrochemical deposition comprises:
(4-1) first pulse electrodeposition wherein the on time of the first positive pulse is set to 10 to 100ms, the off time is set to 89 to 589ms, and the pulse current is set to 30 to 100 mA-cm-2(ii) a The on time of the first negative pulse is set to be 1-10 ms, the off time is set to be 0, and the pulse current is set to be 3-10 mA-cm-2(ii) a The parameters of the first pulse electrodeposition are shown in table 1 first pulse electrodeposition parameter table.
(4-2) second pulse electrodeposition, wherein the on time of the second positive pulse is set to 0.2 to 0.8ms, the off time is set to 0.8 to 0.2ms, and the pulse current is set to 10 to 50 mA-cm-2(ii) a The on time of the first negative pulse is set to be 0.1-0.9 ms, the off time is set to be 0.9-0.1 ms, and the pulse current is set to be 1-5 mA-cm-2The parameters of the second pulse electrodeposition are shown in the second pulse electrodeposition parameter table of Table 2.
TABLE 1 first pulse electrodeposition parameters Table
TABLE 2 second pulse electrodeposition parameters Table
Generally, in the method for manufacturing the electrode for electrochemically degrading aniline disclosed in the embodiment of the application, the first pulse electrodeposition is performed before the second pulse electrodeposition.
Further, as an optional embodiment, the time of the first pulse electrodeposition is set to 15 to 40min, for example, 15min, 20min, 25min, 30min, and the like; the second pulse electrodeposition time is set to 45-120 min, such as 45min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, etc.
As an alternative embodiment, in the electrode manufacturing method for electrochemically degrading aniline, the deposition solution is usually a solution containing tin ions and antimony ions, for example, SnCl2And SbCl3The pH of the solution of (1) is usually adjusted with a suitable buffer. As an alternative embodiment, the deposition solution comprises:
as an optional implementation mode, the titanium substrate covered by the iron-doped titanium dioxide nano array tube deposited with tin and antimony is calcined at the temperature of 500-550 ℃, and the electrode with the antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate structure is obtained.
As an alternative embodiment, an electrode for electrochemical degradation of aniline comprises: a titanium substrate; a layer of titanium dioxide nano array tube is covered on the titanium substrate, wherein iron ions are doped in the titanium dioxide nano array tube; a layer of tin dioxide doped with antimony is deposited on the outer side of the titanium dioxide nano-array tube.
Some embodiments disclose an apparatus for electrochemically degrading aniline, including an electrode for electrochemically degrading aniline disclosed in the embodiments of the present application, typically in an electrochemical apparatus for degrading aniline, the electrode for degrading aniline serves as an anode and a graphite electrode serves as a cathode.
The technical details are further illustrated in the following examples.
Example 1
The preparation method of the electrode for electrochemically degrading aniline, disclosed in example 1, comprises the following steps:
(1) sequentially polishing the surface of a titanium sheet sample by using 600-mesh and 1200-mesh sand paper, ultrasonically cleaning the titanium sheet sample in absolute ethyl alcohol for ten minutes, washing the titanium sheet sample by using deionized water, and then placing the titanium sheet sample in an etching solutionAnd medium etching is carried out for 15s, and the etching liquid comprises the following components: HNO327.43 g/L/L, and then washing with deionized water for standby;
(2) the method comprises the following steps of taking an etched titanium sheet sample as an anode, graphite as a cathode, carrying out anodic oxidation in electrolyte, wherein the anodic oxidation voltage is 25V, the oxidation time is 60min, and the electrolyte comprises the following components: 14g of HF, 350g of ethylene glycol and 650g of deionized water;
(3) after anodic oxidation, taking out a titanium sheet sample, sequentially putting the titanium sheet sample into absolute ethyl alcohol and deionized water for cleaning, and then soaking the titanium sheet sample in 1M FeCl3Soaking in the solution for 5min, washing with deionized water, air drying, and repeating for 5 times; then drying the titanium sheet sample, placing the titanium sheet sample in a muffle furnace, heating to 450 ℃, keeping the temperature for 1h, cooling to room temperature along with the furnace, and taking out for later use;
(4) taking a graphite electrode as an anode, taking a titanium sheet sample covered by the iron-doped titanium dioxide nano array tube prepared in the previous step as a cathode, and performing pulse electrodeposition twice in a deposition solution;
the components of the deposition solution are as follows:
in the first pulse electrodeposition, the on time of the first positive pulse was set to 10ms, the off time was set to 189ms, and the pulse current was set to 100mA · cm-2(ii) a The on time of the first negative pulse was set to 1ms, the off time was set to 0, and the pulse current was set to 10mA · cm-2The first electrodeposition time is 30 min;
in the second pulse electrodeposition, the on time of the second positive pulse was set to 0.2ms, the off time was set to 0.8ms, and the pulse current was set to 40mA · cm-2(ii) a The on time of the first negative pulse was set to 0.1ms, the off time was set to 0.9ms, and the pulse current was set to 4mA · cm-2The second electrodeposition time was 90 min.
Washing the titanium sheet sample obtained by electrodeposition with deionized water at room temperature;
and (3) putting the cleaned titanium sheet sample into a muffle furnace, heating for 2h at 550 ℃, and cooling along with the furnace to obtain the electrode with the antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate structure.
The electrode obtained in example 1 was subjected to a performance test for electrochemically degrading aniline. All solutions used in the test were 0.25MNaSO4And 1 g/L of aniline.
The test result shows that the final oxygen evolution potential is 1.9V, and the electrochemical reaction resistance is 4084.5 omega cm-2In the process of degrading aniline, the concentration is 10mA/cm2Under the current, the groove pressure rises to 0.30V after 2 hours, the predicted service life is 2400 hours at 10mA/cm2Under current, the degradation rate of aniline after 2h is 87%.
Example 2
The preparation method of the electrode for electrochemically degrading aniline, disclosed in example 2, comprises the following steps:
(1) sequentially polishing the surface of a titanium sheet sample by using 600-mesh and 1200-mesh abrasive paper, ultrasonically cleaning for ten minutes in absolute ethyl alcohol, washing with deionized water, and etching for 15 seconds in an etching solution, wherein the etching solution comprises the following components: HNO327.43 g/L/L, and then washing with deionized water for standby;
(2) the method comprises the following steps of taking an etched titanium sheet sample as an anode, graphite as a cathode, carrying out anodic oxidation in electrolyte, wherein the anodic oxidation voltage is 25V, the oxidation time is 30min, and the electrolyte comprises the following components: 13g of HF, 350g of ethylene glycol and 650g of deionized water;
(3) after anodic oxidation, taking out a titanium sheet sample, sequentially putting the titanium sheet sample into absolute ethyl alcohol and deionized water for cleaning, and then soaking the titanium sheet sample in 1M FeCl3Soaking in the solution for 5min, washing with deionized water, air drying, and repeating for 5 times; then drying the titanium sheet sample, placing the titanium sheet sample in a muffle furnace, heating to 400 ℃, keeping the temperature for 1h, cooling to room temperature along with the furnace, and taking out for later use;
(4) taking a graphite electrode as an anode, taking a titanium sheet sample covered by the iron-doped titanium dioxide nano array tube prepared in the previous step as a cathode, and performing pulse electrodeposition twice in a deposition solution;
the components of the deposition solution are as follows:
in the first pulse electrodeposition, the on time of the first positive pulse was set to 10ms, the off time was set to 389ms, and the pulse current was set to 50mA · cm-2(ii) a The on time of the first negative pulse was set to 1ms, the off time was set to 0, and the pulse current was set to 5mA · cm-2The first electrodeposition time is 30 min;
in the second pulse electrodeposition, the on time of the second positive pulse was set to 0.2ms, the off time was set to 0.8ms, and the pulse current was set to 10mA · cm-2(ii) a The on time of the first negative pulse was set to 0.1ms, the off time was set to 0.9ms, and the pulse current was set to 1mA · cm-2The second electrodeposition time was 90 min.
Washing the titanium sheet sample obtained by electrodeposition with deionized water at room temperature;
and (3) putting the cleaned electrode into a muffle furnace, heating for 2 hours at 550 ℃, and cooling along with the furnace to obtain the electrode with the antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate structure.
The electrode obtained in example 2 was subjected to a performance test for electrochemically degrading aniline. All solutions used in the test were 0.25MNaSO4And 1 g/L of aniline.
The test result shows that the final oxygen evolution potential is 2.0V, and the electrochemical reaction resistance is 3543.2 omega cm-2In the process of degrading aniline, the concentration is 10mA/cm2Under the current, the groove pressure rises to 0.35V after 2 hours, the predicted service life is 3400 hours at 10mA/cm2Under current, the degradation rate of aniline after 2h is 84%.
Example 3
The preparation method of the electrode for electrochemically degrading aniline, disclosed in example 3, comprises the following steps:
(1) sequentially polishing the surface of a titanium sheet sample by using 600-mesh and 1200-mesh abrasive paper, ultrasonically cleaning for ten minutes in absolute ethyl alcohol, washing with deionized water, and etching for 15 seconds in an etching solution, wherein the etching solution comprises the following components: HNO327.43 g/L/L, followed by deionizationWashing with water for later use;
(2) taking the etched titanium sheet sample as an anode, taking graphite as a cathode, and carrying out anodic oxidation in electrolyte; the anodic oxidation voltage is 22V, the oxidation time is 30min, and the electrolyte comprises the following components: 12g of HF, 350g of ethylene glycol and 650g of deionized water;
(3) after anodic oxidation, taking out a titanium sheet sample, sequentially putting the titanium sheet sample into absolute ethyl alcohol and deionized water for cleaning, and then soaking the titanium sheet sample in 1M FeCl3Soaking in the solution for 5min, washing with deionized water, air drying, and repeating for 5 times; then drying the titanium sheet sample, placing the titanium sheet sample in a muffle furnace, heating to 450 ℃, keeping the temperature for 1h, cooling to room temperature along with the furnace, and taking out for later use;
(4) taking a graphite electrode as an anode, taking a titanium sheet sample covered by the iron-doped titanium dioxide nano array tube prepared in the previous step as a cathode, and performing pulse electrodeposition twice in a deposition solution;
the components of the deposition solution are as follows:
in the first pulse electrodeposition, the on time of the first positive pulse was set to 10ms, the off time was set to 189ms, and the pulse current was set to 60 mA-cm-2(ii) a The on time of the first negative pulse was set to 1ms, the off time was set to 0, and the pulse current was set to 6mA · cm-2The first electrodeposition time is 30 min;
in the second pulse electrodeposition, the on time of the second positive pulse was set to 0.2ms, the off time was set to 0.8ms, and the pulse current was set to 20mA · cm-2(ii) a The on time of the first negative pulse was set to 0.1ms, the off time was set to 0.9ms, and the pulse current was set to 2mA · cm-2The second electrodeposition time was 90 min.
Washing the titanium sheet sample obtained by electrodeposition with deionized water at room temperature;
and (3) putting the cleaned electrode into a muffle furnace, heating for 2 hours at 550 ℃, and cooling along with the furnace to obtain the electrode with the antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate structure.
The electrode obtained in example 3 was subjected to an aniline electrochemical degradation performance test. All solutions used in the test were 0.25MNaSO4And 1 g/L of aniline.
The test result shows that the final oxygen evolution potential is 2.24V, and the electrochemical reaction resistance is 2084.3 omega cm-2In the process of degrading aniline, the concentration is 10mA/cm2Under the current, the groove pressure rises to 0.15V after 2h, the predicted service life is 4500h at 10mA/cm2Under current, the degradation rate of aniline after 2h is 90%.
Comparative example 1
The preparation method of the electrode for electrochemically degrading aniline disclosed in comparative example 1 includes:
(1) sequentially polishing the surface of a titanium sheet sample by using 600-mesh and 1200-mesh abrasive paper, then ultrasonically cleaning the titanium sheet sample in absolute ethyl alcohol for ten minutes, washing the titanium sheet sample by using deionized water, and etching the titanium sheet sample in an etching solution for 15 seconds; the etching solution comprises the following components: HNO327.43 g/L83.84 g/L, and is washed clean by deionized water for standby;
(2) taking the etched titanium sheet sample as an anode, taking graphite as a cathode, and carrying out anodic oxidation in electrolyte; the anodic oxidation voltage is 25V, the oxidation time is 60min, and the electrolyte comprises the following components: 14g of HF, 350g of ethylene glycol and 650g of deionized water;
(3) after anodic oxidation, taking out a titanium sheet sample, drying, placing in a muffle furnace, heating to 450 ℃, keeping at a constant temperature for 1h, cooling to room temperature along with the furnace, and taking out for later use;
(4) taking a graphite electrode as an anode and a titanium sheet covered by the titanium dioxide nano array tube prepared in the previous step as a cathode, and carrying out direct current deposition in a deposition solution with the current of 20mA/cm2The deposition time is 90 min;
the components of the deposition solution are as follows:
washing the titanium sheet sample obtained by electrodeposition with deionized water at room temperature;
and (3) putting the cleaned electrode into a muffle furnace, heating for 2 hours at 550 ℃, and cooling along with the furnace to obtain the electrode with the antimony-doped tin dioxide/titanium substrate structure.
The electrode obtained in comparative example 1 was subjected to aniline electrochemical degradation test. All solutions tested were 0.25M NaSO4And 1 g/L of aniline.
The test result shows that the final oxygen evolution potential is 2.1V; the electrochemical reaction resistance is 10274 omega cm-2In the process of degrading aniline, the concentration is 10mA/cm2Under the current, the groove pressure rises to 0.35V after 2 hours, the predicted service life is 1200 hours and is 10mA/cm2Under current, the degradation rate of aniline after 2h is 70%.
The electrode manufacturing method for electrochemically degrading aniline, which is disclosed by the embodiment of the application, is characterized in that metal titanium is used as a substrate, iron ions are doped in a titanium dioxide nano array tube, and an antimony-doped tin dioxide catalyst is formed through two pulse electrodeposition, so that the electrode with an antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate base structure is obtained, the charge transfer resistance of the traditional titanium dioxide nano array tube electrode is effectively reduced, the oxygen evolution potential of the electrode is improved, the electrode is used for the electrochemical degradation process of aniline, the electrode structure is stable, the catalytic activity is high, the degradation efficiency is high, the service life is long, and the electrode can also be used for other molecular electrochemical degradation processes with benzene ring structures.
The technical solutions and the technical details disclosed in the embodiments of the present application are only examples to illustrate the concept of the present application, and do not constitute a limitation to the technical solutions of the present application, and all the inventive changes that are made to the technical details disclosed in the present application without inventive changes have the same inventive concept as the present application, and are within the protection scope of the claims of the present application.
Claims (10)
1. A method for manufacturing an electrode for electrochemically degrading aniline is characterized by comprising the following steps:
(1) pretreating a titanium substrate;
(2) taking the pretreated titanium substrate as an anode and graphite as a cathode, and carrying out anodic oxidation reaction in electrolyte to form regularly arranged titanium dioxide nano array tubes on the titanium substrate;
(3) doping iron ions into the titanium dioxide nano array tube to obtain a titanium substrate covered by the iron-doped titanium dioxide nano array tube;
(4) taking a titanium substrate covered by the iron-doped titanium dioxide nano array tube as a cathode, a graphite electrode as an anode and a tin-antimony solution as a deposition solution, and carrying out electrochemical deposition;
(5) and calcining the titanium substrate covered by the iron-doped titanium dioxide nano array tube deposited with tin and antimony at a set temperature to obtain the electrode with the structure of antimony-doped tin dioxide/iron-doped titanium dioxide/titanium substrate.
2. The method for manufacturing an electrode for electrochemical degradation of aniline of claim 1, wherein the pre-treating the titanium substrate comprises:
(1-1) grinding a titanium substrate;
(1-2) cleaning the polished titanium substrate;
(1-3) etching the cleaned titanium substrate in an etching solution, wherein the etching solution is a mixed solution of nitric acid and hydrofluoric acid, the concentration of the nitric acid is 27.43 g/L, and the concentration of the hydrofluoric acid is 83.84 g/L.
3. The method for manufacturing the electrode for electrochemically degrading aniline according to claim 1, wherein the voltage of the anodic oxidation reaction is set to 20-25V, the reaction time is set to 20-90 min, and the electrolyte comprises, by mass, 9-20 parts of HF, 350 parts of ethylene glycol and 650 parts of deionized water.
4. The method for manufacturing an electrode for electrochemically degrading aniline according to claim 1, wherein the doping iron ions into the titanium dioxide nanotubes comprises:
(3-1) placing the titanium substrate covered by the titanium dioxide nano array tube in Fe3+Dipping in the solution for a set time;
(3-2) washing and drying the titanium substrate covered by the dipped titanium dioxide nano array tube;
and (3-3) calcining the titanium substrate covered by the dried titanium dioxide nano array tube at 350-500 ℃ for a set time.
5. The method for manufacturing the electrode for electrochemically degrading aniline of claim 4, wherein the titanium substrate covered by the titanium dioxide nano-array tube is FeCl3The time for dipping in the solution is set to be 3-10 min, and the calcination time of the titanium substrate covered by the dried titanium dioxide nano array tube is set to be 1-2 h.
6. The method for manufacturing an electrode for electrochemical degradation of aniline according to claim 1, wherein the electrochemical deposition comprises:
(4-1) first pulse electrodeposition wherein the on time of the first positive pulse is set to 10 to 100ms, the off time is set to 89 to 589ms, and the pulse current is set to 30 to 100 mA-cm-2(ii) a The on time of the first negative pulse is set to be 1-10 ms, the off time is set to be 0, and the pulse current is set to be 3-10 mA-cm-2；
(4-2) second pulse electrodeposition, wherein the on time of the second positive pulse is set to 0.2 to 0.8ms, the off time is set to 0.8 to 0.2ms, and the pulse current is set to 10 to 50 mA-cm-2(ii) a The on time of the first negative pulse is set to be 0.1-0.9 ms, the off time is set to be 0.9-0.1 ms, and the pulse current is set to be 1-5 mA-cm-2。
7. The method for manufacturing an electrode for electrochemical degradation of aniline according to claim 6, wherein the time for the first pulse electrodeposition is set to 15-40 min, and the time for the second pulse electrodeposition is set to 45-120 min.
8. The method according to claim 1, wherein the deposition solution comprises:
9. an electrode for electrochemically degrading aniline, which is obtained by the method for manufacturing the electrode for electrochemically degrading aniline according to any one of claims 1 to 8, and specifically comprises the following steps:
a titanium substrate;
a layer of titanium dioxide nano array tube is covered on the titanium substrate, wherein iron ions are doped in the titanium dioxide nano array tube;
and a layer of tin dioxide doped with antimony is deposited on the outer side of the titanium dioxide nano-array tube.
10. An apparatus for electrochemically degrading aniline, comprising the electrode for electrochemically degrading aniline of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010252339.6A CN111484104B (en) | 2020-04-01 | 2020-04-01 | Electrode for electrochemically degrading aniline, and electrode manufacturing method and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010252339.6A CN111484104B (en) | 2020-04-01 | 2020-04-01 | Electrode for electrochemically degrading aniline, and electrode manufacturing method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111484104A true CN111484104A (en) | 2020-08-04 |
| CN111484104B CN111484104B (en) | 2021-04-16 |
Family
ID=71791668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010252339.6A Active CN111484104B (en) | 2020-04-01 | 2020-04-01 | Electrode for electrochemically degrading aniline, and electrode manufacturing method and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111484104B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111792706A (en) * | 2020-08-27 | 2020-10-20 | 南京师范大学 | Electrochemical oxidation treatment reactor with cation exchange membrane and method for treating pyridine wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857288A (en) * | 2010-06-18 | 2010-10-13 | 南京理工大学 | Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode |
-
2020
- 2020-04-01 CN CN202010252339.6A patent/CN111484104B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857288A (en) * | 2010-06-18 | 2010-10-13 | 南京理工大学 | Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode |
Non-Patent Citations (1)
| Title |
|---|
| 张孟: "铁掺杂TiO2纳米管阵列的制备与表征及其耐腐蚀性", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111792706A (en) * | 2020-08-27 | 2020-10-20 | 南京师范大学 | Electrochemical oxidation treatment reactor with cation exchange membrane and method for treating pyridine wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111484104B (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Electrocatalytic degradation of methylene blue on Co doped Ti/TiO2 nanotube/PbO2 anodes prepared by pulse electrodeposition | |
| CN102173449A (en) | Method for preparing nanometer lead dioxide electrode | |
| CN109589993B (en) | Electrochemically modified bismuth vanadate-molybdenum sulfide-cobaltosic oxide catalytic electrode and preparation method and application thereof | |
| CN109775813B (en) | Composite intermediate layer for titanium-based oxide electrode, titanium-based oxide electrode and preparation method thereof | |
| CN104386785B (en) | The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode | |
| CN111334837A (en) | Nickel-doped titanium dioxide nanotube modified tin-antimony electrode and preparation method thereof | |
| CN108017120A (en) | A kind of method using Novel anode electrocatalytic oxidation processing phenol organic wastewater | |
| CN113511763B (en) | By TiO 2 -NTs/Sb-SnO 2 /PbO 2 Method for removing ammonia nitrogen in water by electrocatalytic oxidation and application | |
| CN108328703B (en) | Preparation of titanium-based titanium dioxide nanotube deposited tin-antimony-fluorine electrode and application of electrode in chromium-electroplating wastewater chromium fog inhibitor degradation | |
| CN111484104B (en) | Electrode for electrochemically degrading aniline, and electrode manufacturing method and device | |
| CN107653447B (en) | A kind of mineral carbon load stannic oxide electrode and preparation method | |
| CN100368798C (en) | Method for preparing sensor for chemical oxygen demand of Nano tube array and application | |
| CN101894675A (en) | Method for preparing titanium-based super capacitor membrane electrode | |
| CN112520818B (en) | Preparation method and application of metal electrode for reducing nitrate nitrogen in wastewater | |
| Karimi et al. | Novel Ti/TiHx/SnO 2-Sb 2 O 5-NiO-CNT electrode for electrochemical Ozone Generation for degradation of toxic textile azo dyes | |
| Zhang et al. | The effect of Ce doped in Ti/SnO2-Sb2O3/SnO2-Sb2O3-CeO2 electrode and its electro-catalytic performance in caprolactam wastewater | |
| CN102614877B (en) | Preparation method of transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst | |
| CN109824126B (en) | Tin oxide anode electrode with high oxygen evolution potential and preparation method | |
| CN112499729A (en) | Electrode with active layer containing S-doped GO and preparation and application thereof | |
| CN109052574B (en) | Preparation of Ti/SnO based on tricarboxylic organic acid-Sn (II)/Sb (III) complex2Method for producing Sb electrode | |
| CN107902731B (en) | Nickel-boron-fluorine co-doped lead dioxide anode and preparation method and application thereof | |
| CN112250229A (en) | Preparation method and application of electrode with high catalytic activity and stability | |
| CN1667857A (en) | Process for preparing nano structured super platinum film carbon electrodes | |
| CN112429813B (en) | Blue-TiO doped with carbon nano tube 2 /CNT-PbO 2 Preparation method of electrode material | |
| CN111186883B (en) | Novel preparation technology of lead dioxide electrode modified by titanium tetroxide nanotube |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |