CN109264829B - Preparation method of efficient and long-life antimony-doped tin oxide electrode - Google Patents
Preparation method of efficient and long-life antimony-doped tin oxide electrode Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 85
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 76
- 239000006260 foam Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 48
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004729 solvothermal method Methods 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 32
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000004048 modification Effects 0.000 claims abstract description 26
- 238000012986 modification Methods 0.000 claims abstract description 26
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 23
- 238000004321 preservation Methods 0.000 claims abstract description 23
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 23
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- 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
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- 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
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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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C02F2001/46152—Electrodes characterised by the shape or form
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to the technical field of material preparation and water treatment, and aims to provide a preparation method of an antimony doped tin oxide electrode with high efficiency and long service life. The method comprises the following steps: taking SnCl4、SbCl3Taking an alcoholic solution of HCl and a surfactant as a solvothermal reaction solution, immersing the foamed titanium matrix material in the solvothermal reaction solution, carrying out ultrasonic treatment, and carrying out heat preservation reaction at 170-220 ℃; and (3) preserving the temperature at 450-650 ℃ after the reaction, and cooling to obtain the foam titanium substrate antimony doped tin oxide electrode. The method is characterized in that antimony-doped tin oxide electrodes are modified inside and outside a foamed titanium substrate based on a solvothermal reaction, and different catalyst modification amounts, sizes, distribution and shapes are obtained by controlling reaction parameters. According to the invention, the antimony-doped tin oxide particles are uniformly and densely loaded in and out of the porous foam titanium matrix material, and the prepared electrode has excellent pollutant degradation capability and long service life. The method can conveniently regulate and control the modification amount of the catalyst and the size of the catalyst, and has the advantages of simple operation, easy regulation and control, low energy consumption in the preparation process and low cost.
Description
Technical Field
The invention relates to a preparation technology of an electrochemical oxidation anode material, which is mainly applied to an electrochemical advanced oxidation system for treating refractory organic sewage and belongs to the technical field of material preparation and water treatment.
Background
The organic wastewater which is difficult to degrade is one of the problems in the field of water treatment due to high toxicity, high hazard and difficult degradability. The electrochemical advanced oxidation technology can generate substances such as hydroxyl free radicals with strong oxidizing property through the electrocatalytic reaction on the surface of the anode under the condition of lower potential, and the pollutants are removed by utilizing the reaction of the free radicals and the organic pollutants which are difficult to degrade; no extra chemical is needed in the treatment process, and the reaction condition is mild; has the advantages of high efficiency, low cost, simple operation, easy expansion and the like, and has great application prospect in the field of treatment of organic wastewater difficult to degrade.
The electrode material directly influences the treatment effect of the electrochemical oxidation technology. The electrode material commonly used at present comprises Ti/RuO2、Ti/IrO2Carbon material electrode, lead dioxide (PbO)2) Electrodes, boron doped diamond thin film electrodes (BDD) electrodes, antimony doped tin oxide (ATO) electrodes, and the like. Of these materials, Ti/RuO2、Ti/IrO2The carbon material electrode has low oxygen evolution potential and free radical yield, and poor pollutant degradation capability. And PbO2The preparation and use processes of the electrode can release Pb ions to cause heavy metal pollution. The BDD electrode has complex preparation process, high preparation energy consumption and expensive electrode cost. Compared with the electrodes, the ATO electrode has the advantages of simple preparation process, low price, low toxicity and the like, however, the ATO electrode prepared by the traditional method is limited by the base material and the electrode preparation method, the prepared electrode usually has low modification amount, the service life of the electrode is very short, and the practical application of the ATO electrode is greatly limited.
The traditional ATO electrode mainly adopts a dipping method, a solution-gel method and an electrodeposition method to modify an antimony doped tin oxide catalyst on a Ti sheet or Ti net substrate. Wherein, the dipping method and the solution-gel method need to repeatedly carry out the processes of coating, drying and high-temperature burning in the preparation process, the preparation efficiency of the electrode is low, the energy consumption is high, and the process is complicated; in the heating and burning process, as the solvent is evaporated, the surface of the electrode can form a chapped structure, which aggravates the dissolution and falling of the catalyst and influences the service life of the electrode. When the modification amount of the catalyst is increased, on one hand, the preparation time and the energy consumption of the electrode are multiplied; on the other hand, the unevenness of the electrode surface is increased, and the plating layer is peeled off. For preparing the ATO electrode by the electrodeposition method, the combination of the modification layer and the substrate material is poor, the catalyst layer is easy to fall off in the preparation and use processes along with the improvement of the modification amount, and on the other hand, the conductivity of the electrode is poor, the performance of the electrode is reduced, so that the method is not suitable for preparing the ATO electrode with high modification amount.
The solvothermal reaction modification method is a novel material preparation method, and has the advantages of simple operation, high reaction speed, mild conditions, good dispersibility of prepared products, high crystallinity, controllable granularity and the like. Compared with the traditional titanium sheet or titanium mesh material, the foamed titanium material rich in micropores has high specific surface area, and the inner part and the outer part can provide attachment sites for the catalyst, so that the foamed titanium material is a suitable substrate material for the antimony-doped tin oxide electrode. The method is based on a solvothermal reaction modification method, and the ATO catalyst is uniformly and densely loaded on the surface and the interior of the foamed titanium matrix material, so that the electrode material with high performance, long service life and low cost is prepared; the modification amount, the size, the distribution morphology and the like of the catalyst can be conveniently regulated and controlled by controlling the concentration and the components of the solvothermal reaction solution, the reaction temperature, the reaction time and the like. The method has the advantages of simple preparation process, low preparation cost and low pollution in the preparation process, and can be applied to the practical production of the electrochemical oxidation electrode with high efficiency and long service life.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior preparation technology and provides a preparation method of an antimony doped tin oxide electrode with high efficiency and long service life by taking titanium foam as a base material.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the antimony doped tin oxide electrode with high efficiency and long service life is provided, the antimony doped tin oxide electrode is modified inside and outside the foamed titanium substrate based on the solvothermal reaction, and different catalyst modification amounts, sizes, distribution and shapes are obtained by controlling reaction parameters; the method specifically comprises the following steps:
(1) taking SnCl4、SbCl3Placing an alcoholic solution of HCl and a surfactant in a hydrothermal kettle to be used as a solvothermal reaction solution; in a solvothermal reaction solution, SnCl4·5H2The molar concentration of O is 0.2-1.5 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.09-0.03; the molar concentration of the hydrochloric acid is 0.6-2.4 mol/L; the concentration of the surfactant is 0-0.3 mol/L;
(2) immersing the pretreated foam titanium matrix material in a solvothermal reaction solution, and carrying out ultrasonic treatment for 5 min; sealing the hydrothermal kettle, and then carrying out heat preservation reaction for 8-36 h at the temperature of 170-220 ℃; cooling to room temperature after the reaction is finished, taking out the hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, and preserving heat for 1-3 h at the temperature of 450-650 ℃; and cooling to room temperature after heat preservation is finished to obtain the foam titanium substrate antimony doped tin oxide electrode.
In the invention, the pretreatment of the titanium foam refers to: sequentially polishing with 400-mesh and 800-mesh sand paper, and cleaning with deionized water; then soaking the mixture in NaOH solution with the mass concentration of 40 wt% at the temperature of 80 ℃ for 0.5h, taking out and washing the mixture with deionized water; then the mixture is transferred to an oxalic acid solution with the mass concentration of 10 wt% to be boiled for 0.5h, cleaned under the ultrasonic condition and soaked in an ethanol solution for standby.
In the invention, the muffle furnace in the step (2) adopts program control heating, and the heating rate is 1-25 ℃/min.
In the invention, the solvent thermal reaction liquid takes methanol, ethanol or ethylene glycol as a solvent.
In the invention, the surfactant is any one of citric acid, glucose or sodium dodecyl sulfate.
In the invention, when the titanium foam matrix material is immersed in the solvent hot reaction liquid, the titanium foam matrix material is obliquely placed. The inclined immersion is beneficial to improving the adhesion amount of the catalyst on the foamed titanium substrate, the catalyst can grow on the base material without being obliquely placed, and the inclination angle is not required.
Description of the inventive principles:
the invention takes alcohol as solvent, under the condition of specific reaction temperature, the solvent is evaporated in a closed reaction kettle to form high-pressure environment, which is beneficial to reducing reaction activation energy and chemical reaction barrier, so that SnCl is realized under the condition of relatively low temperature4And SbCl3With O in a closed environment2Reacting to separate out antimony doped tin oxide particles. Wherein, the formation of tin oxide crystal mainly passes through nucleation and growth stages, and in the nucleation stage, the system overcomes energy obstacle in a microscopic small area of a two-phase interface of the titanium foam and the reaction solution to formA new phase nucleus of stabilized tin oxide; after the new phase is formed, a transition zone between the new phase and the old phase with higher free energy appears nearby, and the reaction is carried out at the interface of the crystal nucleus and the solution, so that the crystal nucleus grows gradually. The foamed titanium material is rich in micropores inside, and the inside and the outside of the foamed titanium material can provide sites for nucleation and growth, so that the antimony-doped tin oxide catalyst can be loaded inside and outside the foamed titanium material simultaneously.
The nucleation and growth processes of the antimony-doped tin oxide grains can be influenced by factors such as the concentration of the reaction solution, the type of the solvent, the pH, the reaction temperature and the reaction time, so that the modification amount, the morphology, the distribution, the size and the like of the catalyst can be regulated and controlled by controlling the factors such as the concentration, the components, the reaction temperature and the reaction time of the reaction solution. On the other hand, the thickness of the ion diffusion layer is limited by the high-pressure environment, the crystal grains can be prevented from being rapidly generated while being rapidly synthesized, and the possibility of effectively controlling the content, the size and the shape of the catalyst is provided.
The electrode catalyst prepared by the method can be uniformly and densely loaded in the foam titanium substrate and on the outer surface of the foam titanium substrate, the catalyst layer has good coating capacity on the Ti substrate, and the performance and stability of the electrode can be prevented from being reduced due to the bare oxidation of Ti sheets; the catalyst has high specific surface area, is beneficial to generating higher concentration of free radicals in the degradation process and promoting the degradation of pollutants; the finally prepared electrode shows excellent degradation performance and long life.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional impregnation method, the solution gel method and the electrodeposition method, the method can realize the uniform and dense loading of the antimony-doped tin oxide particles inside and outside the porous foam titanium matrix material, and the prepared electrode has excellent pollutant degradation capability and long service life.
2. The method can conveniently regulate and control the proper modification amount of the catalyst to be 15-450 mg/cm2(ii) a Overcomes the defects of low catalyst modification amount, difficult regulation and control and the like in the traditional method.
3. The method can conveniently regulate and control the size of the catalyst to be between 500nm and 3000 nm; the prepared catalyst has high specific surface area and electrochemical activity.
4. The method disclosed by the invention is simple to operate, easy to regulate and control, low in energy consumption and low in cost in the preparation process, and can be suitable for actually producing the efficient and long-life three-dimensional antimony-doped tin oxide electrode.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the prepared electrode with a solvothermal reaction time of 12h and a surface magnification of 5000 in example 2.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the electrode prepared by adding citric acid in example 3 at a surface magnification of 5000.
Fig. 3 is an X-ray diffraction pattern (XRD) of the electrodes prepared in embodiment 2 and embodiment 3.
FIG. 4 is a degradation curve of methylene blue simulated wastewater treated by titanium foam substrate ATO electrode materials prepared by different methods in specific example 4, comparative example 1 and comparative example 2.
Detailed Description
The invention is further described with reference to the following figures and specific examples, which are intended to better illustrate the invention and not to limit it.
Detailed description of the preferred embodiment 1
The method is adopted to prepare the three-dimensional antimony doped tin oxide electrode which takes the titanium foam with different specifications as the substrate material.
Selecting foamed titanium materials with the size of 20mm multiplied by 20mm and the thickness of 0.4mm (aperture 10 mu m), 1.5mm (aperture 150 mu m), 5mm (aperture 200 mu m) and 10mm (aperture 300 mu m), and respectively using two foamed titanium materials in each specification (the final product is respectively used for methylene blue simulated wastewater degradation test and electrode accelerated life test); sequentially polishing with 400-mesh and 800-mesh sand paper, cleaning with deionized water, and soaking in 40 wt% NaOH solution at 80 deg.C for 0.5 h; after soaking, washing with deionized water, and boiling in oxalic acid solution with the mass concentration of 10 wt% for 0.5 h; then ultrasonically cleaning and soaking in an ethanol solution for later use.
Preparing four portions of solvent thermal reaction liquid, wherein each portion of solvent thermal reaction liquidThe configuration method comprises the following steps: absorbing 3mL of concentrated hydrochloric acid with the mass concentration of 37.5 percent, dropwise adding the concentrated hydrochloric acid into 27mL of ethanol solvent, and uniformly mixing; weighing 4.2g SnCl4·5H2O、0.25gSbCl3Adding the mixture into a mixed solution of ethanol and hydrochloric acid, and uniformly stirring until a clear solution is formed; in the solvothermal reaction liquid, the molar concentration of hydrochloric acid is 1.2 mol/L; SnCl4·5H2The molar concentration of O is 0.4 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.09.
Obliquely immersing the pretreated titanium foam substrate material in a solvent thermal reaction solution respectively, performing ultrasonic treatment for 5min, sealing a hydrothermal kettle at 180 ℃, performing heat preservation reaction for 36h, cooling to room temperature, taking out, placing in a muffle furnace, performing heat preservation for 2h at 550 ℃, performing program-controlled temperature rise in the muffle furnace at the temperature rise rate of 1 ℃/min, and cooling to room temperature after heat preservation is completed to obtain the antimony doped tin oxide electrode with the titanium foam substrate, wherein the antimony doped tin oxide electrode has high performance and long service life.
The catalyst modification amounts of the antimony doped tin oxide electrodes taking the foam titanium with the thickness of 0.4mm, 1.5mm, 5mm and 10mm as the substrate material are respectively 15mg/cm2、70mg/cm2、190mg/cm2And 450mg/cm2. Catalyst modification amount the catalyst modification amount can be known by accurately weighing the mass of the foamed titanium substrate material before and after modification.
The electrode prepared in example 1 was used for methylene blue simulated wastewater degradation testing, and the testing experiment steps were:
preparing Methylene Blue (MB) solution with the concentration of 100mg/L, and adding 0.25M Na2SO4Adjusting the conductivity, and adding the solution into an electrolytic cell with the volume of 120 ml; the anode of the electrolytic cell adopts a prepared ATO electrode, the cathode adopts a platinum sheet electrode with the size of 20mm multiplied by 20mm, the distance between the anode and the cathode is 2cm, and the stirring speed of a rotor at the bottom of the electrolytic cell is 500 rpm; the degradation current density is 20mA/cm2. Sampling from the electrolytic cell by using a liquid-transferring gun at regular time and analyzing (0h, 1h, 2h, 3h and 4 h); fitting the degradation result of MB by adopting first-level degradation kinetics, and performing first-level degradation on the antimony-doped tin oxide electrode prepared by using foamed titanium with the thicknesses of 0.4mm, 1.5mm, 5mm and 10mm as substratesThe rate constants are respectively 0.92h-1、0.96h-1、1.13h-1And 0.98h-1(ii) a The foamed titanium substrate antimony doped tin oxide electrode prepared based on the method provided by the invention has excellent pollutant degradation performance.
The electrode prepared in example 1 was subjected to an accelerated life test by subjecting H at a concentration of 0.5M2SO4Adding the solution into an electrolytic cell for accelerated life test, wherein the anode adopts a prepared electrode, the cathode adopts a platinum sheet electrode with the size of 20mm multiplied by 20mm, and the test electrolytic current density is 100mA/cm2And recording the voltages at two ends of the cathode and the anode by using a data acquisition instrument, wherein the data acquisition interval is 5min, when the voltages at two ends of the cathode and the anode rise to 10V, the electrode is considered to be invalid, and the recorded electrolysis time is the accelerated life time of the test electrode. The accelerated lives of the antimony doped tin oxide electrodes prepared by taking foamed titanium with the thicknesses of 0.4mm, 1.5mm, 5mm and 10mm as substrates are respectively 86h, 200h, 300h and 380 h; the electrode prepared by the method has long service life.
Specific example 2
By adopting the method, the modification amount and the size of the antimony doped tin oxide electrode catalyst taking the foamed titanium as the substrate material are regulated and controlled by controlling different solvothermal reaction times.
Selecting four foam titanium materials with the sizes of 20mm multiplied by 0.8mm and the aperture of 50 mu m, sequentially polishing the foam titanium materials by 400-mesh and 800-mesh abrasive paper, cleaning the foam titanium materials by deionized water, and soaking the foam titanium materials in NaOH solution with the mass concentration of 40 wt% for 0.5h at the temperature of 80 ℃; after soaking, washing with deionized water, and boiling in oxalic acid solution with the mass concentration of 10 wt% for 0.5 h; then ultrasonically cleaning and soaking in an ethanol solution for later use.
Preparing four portions of solvothermal reaction liquid, wherein the preparation method of the solvothermal reaction liquid comprises the steps of sucking 1.5mL of concentrated hydrochloric acid with the mass concentration of 37.5 percent, dropwise adding the concentrated hydrochloric acid into 28.5mL of ethanol solvent, and uniformly mixing; 6.3g SnCl are weighed out4·5H2O、0.188gSbCl3Adding the mixture into a mixed solution of ethanol and hydrochloric acid, and uniformly stirring until a clear solution is formed; in the solvothermal reaction liquid, the molar concentration of hydrochloric acid is 0.6 mol/L; SnCl4·5H2The molar concentration of O is 0.4 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.045.
Obliquely immersing the pretreated titanium foam substrate material in a solvent thermal reaction solution respectively, performing ultrasonic treatment for 5min, sealing a hydrothermal kettle at 200 ℃, performing heat preservation reaction for 8h, 12h, 24h and 36h respectively, cooling to room temperature, taking out, placing in a muffle furnace, performing heat preservation for 3h at 450 ℃, raising the temperature of the muffle furnace by program control at a rate of 5 ℃/min, and cooling to room temperature after heat preservation is completed to obtain the antimony doped tin oxide electrode with the titanium foam substrate, wherein the antimony doped tin oxide electrode has high performance and long service life. The catalyst modification amounts of the electrodes with the reaction time of 8h, 12h, 24h and 36h are respectively 13mg/cm2、16mg/cm2、31mg/cm2、46mg/cm2(ii) a The electrode modification amount is in positive correlation with the solvothermal reaction time, and the electrode modification amount can be regulated and controlled by controlling the solvothermal reaction time.
Characterization of the electrode of the invention:
observing the surface of a foam titanium substrate antimony doped tin oxide electrode prepared with solvothermal reaction time of 36h and 12h by using a scanning electron microscope (see figure 1), wherein the solvothermal reaction time is 36h, the catalyst on the surface of the prepared electrode is distributed in a hollow ellipsoid or hemisphere shape, the size is 2-3 mu m, the internal pore diameter is about 1 mu m, the shape of the catalyst is complete, and the catalyst is uniformly distributed; the solvothermal reaction time is 12 hours, the prepared electrode surface is in uniform and large ellipsoidal distribution, the size of the prepared electrode is smaller than the solvothermal reaction time and is 36 hours, and the size of the prepared electrode is 0.5-1.8 mu m; the size of the catalyst can be regulated and controlled by controlling the reaction time.
And (3) carrying out XRD characterization on the electrodes prepared by different solvent thermal reaction times by using an X-ray diffractometer, and obtaining an XRD spectrogram (see figure 3). The XRD pattern of the sample completely conforms to diffraction peaks of a tetragonal tin dioxide standard card at 2 theta (26.597 degrees), 33.889 degrees, 37.968 degrees, 38.994 degrees, 42.655 degrees, 51.795 degrees, 54.78 degrees, 57.852 degrees, 61.908 degrees, 62.629 degrees, 64.767 degrees, 65.994 degrees, 69.272 degrees, 71.308 degrees, 74.481 degrees and 78.744 degrees, which indicates that the modifier is tetragonal tin dioxide, and related diffraction peaks of antimony do not appear, indicating that antimony is successfully doped into tin dioxide lattices, and related diffraction peaks of Ti do not appear, indicating that the modification layer on the surface of the electrode is compact, and can completely cover a titanium substrate, and the improvement of the stability of the electrode is facilitated. As the solvothermal reaction time is prolonged, the XRD diffraction peak intensity is increased, and the diffraction peak width is narrowed, which indicates that the size and the crystallinity of the catalyst are increased; therefore, the size and crystallinity of the catalyst can be regulated and controlled by controlling the solvothermal reaction time.
Specific example 3
By adopting the method, the antimony doped tin oxide electrode taking the titanium foam as the matrix material is prepared by taking methanol as a reaction solution solvent and adding citric acid as a surfactant.
Selecting a foamed titanium material with the size of 20mm multiplied by 20mm, sequentially polishing by 400-mesh and 800-mesh abrasive paper, cleaning by deionized water, and soaking in a NaOH solution with the mass concentration of 40 wt% at 80 ℃ for 0.5 h; after soaking, washing with deionized water, and boiling in oxalic acid solution with the mass concentration of 10 wt% for 0.5 h; then ultrasonically cleaning and soaking in an ethanol solution for later use.
The preparation method of the solvothermal reaction solution comprises the steps of sucking 6mL of concentrated hydrochloric acid with the mass concentration of 37.5 percent, dropwise adding the concentrated hydrochloric acid into 24mL of methanol solvent, and uniformly mixing; 6.3g SnCl are weighed out4·5H2O、0.125g SbCl31.73g of citric acid is added into the mixed solution of ethanol and hydrochloric acid, and the mixture is uniformly stirred until a clear solution is formed; in the solvothermal reaction liquid, the molar concentration of hydrochloric acid is 2.4 mol/L; SnCl4·5H2The molar concentration of O is 0.6 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.03; the molar concentration of the citric acid is 0.3 mol/L.
Obliquely immersing the pretreated titanium foam substrate material in a solvent thermal reaction solution respectively, performing ultrasonic treatment for 5min, sealing a hydrothermal kettle at 210 ℃, performing heat preservation reaction for 24h, cooling to room temperature, taking out, placing in a muffle furnace, performing heat preservation for 1h at 650 ℃, raising the temperature of the muffle furnace by program control at a rate of 5 ℃/min, and cooling to room temperature after heat preservation is finished to obtain a high-performance long-life antimony-doped tin oxide electrode with a titanium foam substrate; the method prepares electricityThe modification amount of the electrode is about 20mg/cm2。
Characterization of the electrode of the invention:
the electrode surface is observed by using a scanning electron microscope (see figure 2), so that the added citric acid is taken as a surfactant, and the flatness of the electrode surface is increased, which is beneficial to improving the coverage of a catalyst on a base material and improving the stability of the electrode; XRD characterization of the electrode was performed using an X-ray diffractometer (see FIG. 3), and the diffraction peak of the electrode prepared using citric acid as a surfactant was broadened, indicating that the catalyst size and crystallinity were reduced.
Specific example 4
By adopting the method, the antimony doped tin oxide electrode taking the titanium foam as the matrix material is prepared by taking ethylene glycol as a reaction solution solvent and adding glucose as a surfactant.
Selecting a foamed titanium material with the size of 20mm multiplied by 20mm, sequentially polishing by 400-mesh and 800-mesh abrasive paper, cleaning by deionized water, and soaking in a NaOH solution with the mass concentration of 40 wt% at 80 ℃ for 0.5 h; after soaking, washing with deionized water, and boiling in oxalic acid solution with the mass concentration of 10 wt% for 0.5 h; then ultrasonically cleaning and soaking in an ethanol solution for later use.
The preparation method of the solvothermal reaction solution comprises the steps of sucking 3mL of concentrated hydrochloric acid with the mass concentration of 37.5 percent, dropwise adding the concentrated hydrochloric acid into 27mL of methanol solvent, and uniformly mixing; weighing 8.4g SnCl4·5H2O、0.5g SbCl30.54g of glucose is added into the mixed solution of ethanol and hydrochloric acid, and the mixture is uniformly stirred until a clear solution is formed; in the solvothermal reaction liquid, the molar concentration of hydrochloric acid is 1.2 mol/L; SnCl4·5H2The molar concentration of O is 0.8 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.09; the molar concentration of glucose was 0.1 mol/L.
Obliquely immersing the pretreated foam titanium matrix material in a solvothermal reaction solution respectively, performing ultrasonic treatment for 5min, sealing a hydrothermal kettle at 220 ℃, performing heat preservation reaction for 8h, cooling to room temperature, taking out, placing in a muffle furnace, performing heat preservation for 1h at 650 ℃, and raising the temperature of the muffle furnace by program control at a rate of15 ℃/min, cooling to room temperature after heat preservation is finished to obtain the foam titanium substrate antimony doped tin oxide electrode with high performance and long service life, wherein the modification amount of the electrode prepared by the method is about 13mg/cm2。
The methylene simulation wastewater degradation test is carried out by adopting the electrode disclosed by the invention, the specific steps of the test are the same as those of the specific example 1, and the methylene blue degradation curve is shown in a figure 5. It can be seen that the electrode of the invention shows excellent pollutant degradation performance, the first-level degradation kinetic fitting is carried out on the degradation result, and the first-level degradation kinetic constant reaches 0.91h-1。
Specific example 5
By adopting the method, ethanol is used as a reaction solution solvent, sodium dodecyl sulfate is added as a surfactant, and the antimony doped tin oxide electrode taking titanium foam as a matrix material is prepared.
The preparation method of the solvothermal reaction solution comprises the steps of sucking 6ml of concentrated hydrochloric acid with the mass concentration of 37.5 percent, dropwise adding the concentrated hydrochloric acid into 24ml of ethanol solvent, and uniformly mixing; 15.8g SnCl was weighed4·5H2O、0.94g SbCl30.43g of sodium dodecyl sulfate is added into the mixed solution of ethanol and hydrochloric acid, and the mixture is uniformly stirred until a clear solution is formed; in the solvothermal reaction liquid, the molar concentration of hydrochloric acid is 2.4 mol/L; SnCl4·5H2The molar concentration of O is 1.5 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.09; the molar concentration of the sodium dodecyl sulfate is 0.05 mol/L.
Obliquely immersing the pretreated titanium foam substrate material in a solvent thermal reaction solution respectively, performing ultrasonic treatment for 5min, sealing a hydrothermal kettle at 170 ℃, performing heat preservation reaction for 16h, cooling to room temperature, taking out, placing in a muffle furnace, performing heat preservation for 1h at 650 ℃, raising the temperature of the muffle furnace by program control at a rate of 5 ℃/min, and cooling to room temperature after heat preservation is finished to obtain a high-performance long-life antimony-doped tin oxide electrode with a titanium foam substrate; the modification amount of the electrode is about 38mg/cm2。
Specific example 6
By adopting the method, the antimony doped tin oxide electrode taking the titanium foam as the matrix material is prepared by taking methanol as a reaction solution solvent and not adding a surfactant.
The preparation method of the solvothermal reaction solution comprises the steps of sucking 3mL of concentrated hydrochloric acid with the mass concentration of 37.5 percent, dropwise adding the concentrated hydrochloric acid into 27mL of ethanol solvent, and uniformly mixing; weighing 2.1g SnCl4·5H2O、0.125g SbCl3Adding the mixture into a mixed solution of ethanol and hydrochloric acid, and uniformly stirring until a clear solution is formed; in the solvothermal reaction liquid, the molar concentration of hydrochloric acid is 1.2 mol/L; SnCl4·5H2The molar concentration of O is 0.2 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.09.
Obliquely immersing the pretreated titanium foam substrate material in a solvent thermal reaction solution respectively, performing ultrasonic treatment for 5min, sealing a hydrothermal kettle at 170 ℃, performing heat preservation reaction for 36h, cooling to room temperature, taking out, placing in a muffle furnace, performing heat preservation for 1h at 650 ℃, performing program-controlled temperature rise in the muffle furnace at a temperature rise rate of 25 ℃/min, and cooling to room temperature after heat preservation to obtain the antimony doped tin oxide electrode with the titanium foam substrate, which has high performance and long service life.
Comparative example 1
An antimony doped tin oxide electrode with foamed titanium as a base material is prepared by adopting an impregnation method, and the method comprises the following specific steps: selecting foamed titanium with the specification of 20mm multiplied by 0.8mm as a base material of the electrode; the pretreatment of the titanium foam was carried out as in example 1.
The preparation method of the dipping solution comprises the following steps: 17.52g SnCl were weighed4·5H2O；0.18g SbCl3Dissolving in 50ml of isopropanol solvent, and dropwise adding 2ml of concentrated hydrochloric acid to promote dissolution; soaking the pretreated titanium foam in the dipping solution, carrying out ultrasonic treatment for 2min, taking out, drying in a drying oven at 100 ℃ for 10min, baking in an air atmosphere in a muffle furnace at 550 ℃ for 10min, taking out and cooling; repeating the steps of dipping, ultrasonic treatment, drying and baking for 9 times, baking the finally prepared electrode at 550 ℃ for 60min, and taking out the electrode to obtain the antimony doped tin oxide electrode which is prepared by the dipping method and takes the titanium foam as the substrate material. The modification amount of the electrode is 4.2mg/cm2The catalyst is mainly distributed in the foamed titanium matrixThe surface distribution amount of the substrate is very low.
The methylene simulation wastewater degradation test for preparing the electrode is carried out in the same specific experimental steps as in the specific example 1, and the methylene blue degradation curve is shown in figure 4; performing first-stage degradation kinetic fitting on the degradation result, wherein the first-stage degradation kinetic constant of the first-stage degradation kinetic fitting is 0.62h-1(ii) a The electrode accelerated life test is carried out on the prepared electrode, the specific operation steps are the same as those of the specific example 1, and the electrode accelerated life is 34 h.
Comparative example 2
An electrodeposition method is adopted to prepare the antimony doped tin oxide electrode taking titanium foam as a substrate material, and the specific steps are as follows: selecting foamed titanium with the specification of 20mm multiplied by 0.8mm as a base material of the electrode; the pretreatment of the titanium foam was carried out as in example 1.
The preparation method of the electrodeposition solution comprises weighing 2.6g SnCl4·5H2O；0.164g SbCl3And 1.2g tartaric acid dissolved in 80ml deionized water; the electrodeposition process comprises the following steps: vertically immersing pretreated titanium foam into an electrodeposition solution to serve as a working electrode, symmetrically arranging graphite sheets with the diameter of 3.5cm on two sides of the titanium foam to serve as counter electrodes, connecting a power supply anode and the counter electrodes, connecting a power supply cathode and the working electrode, setting the deposition current to be 40mA, and setting the electrodeposition time to be 20 min; and after the electrodeposition is finished, naturally airing at room temperature, then transferring into a muffle furnace to bake for 3 hours at 600 ℃, wherein the muffle furnace adopts program control heating, the heating rate is 5 ℃/min, and cooling to room temperature to obtain the antimony doped tin oxide electrode which is prepared by the electrodeposition method and takes the titanium foam as the substrate. The modified amount of the catalyst of the electrode is about 10mg/cm2(ii) a The catalyst is mainly distributed on the surface of the titanium foam, and the distribution amount in the titanium foam is extremely low.
Carrying out methylene simulation wastewater degradation test on the prepared electrode, wherein the specific experimental steps are the same as those of the specific example 1, and a methylene blue degradation curve is shown in a figure 4; performing first-stage degradation kinetic fitting on the degradation result, wherein the first-stage degradation kinetic constant is 0.45h-1(ii) a The accelerated electrode life test is carried out on the prepared electrode, the specific operation steps are the same as those of the specific example 1, and the accelerated electrode life is 5 hours.
Claims (3)
1. A preparation method of an antimony-doped tin oxide electrode with high efficiency and long service life is characterized in that the antimony-doped tin oxide electrode is modified inside and outside a foamed titanium substrate based on solvothermal reaction, and different catalyst modification amounts, sizes, distribution and shapes are obtained by controlling reaction parameters; the method specifically comprises the following steps:
(1) taking SnCl4、SbCl3Placing an alcoholic solution of HCl and a surfactant in a hydrothermal kettle to be used as a solvothermal reaction solution; in a solvothermal reaction solution, SnCl4·5H2The molar concentration of O is 0.2-1.5 mol/L; SbCl3With SnCl4·5H2The molar concentration ratio of O is 1: 0.09-0.03; the molar concentration of the hydrochloric acid is 0.6-2.4 mol/L; the surfactant is any one of citric acid, glucose or sodium dodecyl sulfate, and the concentration of the surfactant is 0.05-0.3 mol/L;
(2) obliquely placing the pretreated foam titanium matrix material, immersing the pretreated foam titanium matrix material in a solvothermal reaction solution, and carrying out ultrasonic treatment for 5 min; sealing the hydrothermal kettle, and then carrying out heat preservation reaction for 8-36 h at the temperature of 170-220 ℃; cooling to room temperature after the reaction is finished, taking out the hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, and preserving heat for 1-3 h at the temperature of 450-650 ℃; the muffle furnace adopts program control heating, and the heating rate is 1-25 ℃/min; and cooling to room temperature after heat preservation is finished to obtain the foam titanium substrate antimony doped tin oxide electrode.
2. The method according to claim 1, wherein the pretreatment of the titanium foam is: sequentially polishing with 400-mesh and 800-mesh sand paper, and cleaning with deionized water; then soaking the mixture in NaOH solution with the mass concentration of 40 wt% at the temperature of 80 ℃ for 0.5h, taking out and washing the mixture with deionized water; then the mixture is transferred to an oxalic acid solution with the mass concentration of 10 wt% to be boiled for 0.5h, cleaned under the ultrasonic condition and soaked in an ethanol solution for standby.
3. The method according to claim 1, wherein the solvothermal reaction solution is methanol, ethanol or ethylene glycol as a solvent.
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