CN115957604A - Carbon nanotube modified carbon cloth electrode with adjustable structure and preparation method and application thereof - Google Patents
Carbon nanotube modified carbon cloth electrode with adjustable structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon nanotube modified carbon cloth electrode with an adjustable structure and a preparation method and application thereof. According to the method, a carbon cloth is used as a substrate, transition metal nitrate is used as a catalyst, methylbenzene is used as a carbon source, water vapor is used as a reducing agent and a growth promoter, a precursor solution consisting of the methylbenzene and water is vaporized and injected into a high-temperature tube furnace, the growth density, the length and surface functional groups of the carbon nano tube are regulated and controlled by adjusting parameters such as catalyst concentration, water vapor content, carrier gas flow rate, precursor solution injection speed and reaction time, and the adsorption and electrocatalysis performance of the obtained electrode is further promoted; the invention has mild reaction condition and simple preparation method. The prepared carbon nano tube modified carbon cloth electrode is used for carrying out adsorption-electrooxidation on the oxygen-containing volatile organic compounds, so that the excellent degradation performance of rapid degradation after adsorption is realized, the degradation performance and the electrode stability of the refractory oxygen-containing volatile organic compounds are greatly improved, and the carbon nano tube modified carbon cloth electrode can be widely applied to treatment of the refractory volatile organic compounds.
Description
Technical Field
The invention belongs to the technical field of air pollution control, relates to a nano material preparation technology and an adsorption-electrochemical oxidation treatment technology of nondegradable oxygen-containing volatile organic compounds, and particularly relates to a carbon nano tube modified carbon cloth electrode with an adjustable structure as well as a preparation method and application thereof.
Background
The discharge of toxic, high-molecular and difficultly-degraded oxygen-containing volatile organic compounds in the Volatile Organic Compounds (VOCs) provides challenges for traditional treatment methods such as adsorption, absorption and microorganisms. Therefore, it is necessary to develop a treatment method with good environmental compatibility, small floor space and strong oxidation capability. Electrochemical oxidation has been successfully used as an advanced treatment system for the study of refractory organic pollutants.
Anodization is considered an effective technique to decompose even the most difficult organic pollutants to degrade. Carbon nanotubes are widely used for anode modification due to their unique electrical conductivity, porous structure and controllable surface electrochemical properties. In addition, the in-situ grown CNT can regulate the electrocatalytic performance through preparation conditions, and the problems of poor apparent catalytic activity and poor working stability caused by methods such as coating, electrophoretic deposition and the like are also avoided. Chinese patent CN 113044830A discloses a method for preparing an in-situ grown carbon nanotube/graphene composite sponge, wherein the morphology of the carbon nanotube is regulated and controlled by adjusting the concentration of nickel nitrate and the vapor deposition time, and the electrical conductivity and the composite mechanical property are improved at the same time. Chinese patent CN 110067004A introduces a method for growing CNTs in situ on carbon cloth, firstly loading a catalyst on the carbon cloth through hydrothermal reaction, and then performing chemical vapor deposition to generate carbon nanotubes, thereby enhancing electrocatalytic activity and working stability. The preparation method takes hydrogen as reducing gas, has large potential safety hazard in operation, and is complex in preparation method and complex in process.
Meanwhile, the carbon nano tube shows remarkable adsorbability and is commonly used for adsorbing and enriching organic pollutants. Chinese patent CN 109092245A introduces a method for preparing a diatomite-loaded carbon nanotube adsorbent, which comprises mixing diatomite as a substrate with a catalyst, vacuum-filtering, and adsorbing phenolic organic substances with the adsorbent prepared from nitrogen, hydrogen and a carbon source (acetylene, methane or carbon monoxide).
However, the carbon anode has a lower oxygen evolution potential, so that a large amount of hydroxyl radicals are adsorbed on the surface of the anode after being generated, and more hydroxyl radicals participate in the oxygen evolution reaction, thereby resulting in lower organic matter degradation efficiency. At present, researches on improving the degradation efficiency of the carbon electrode on organic pollutants by a method combining adsorption and electrooxidation are only reported, but researches on application of a carbon nano tube modified carbon cloth electrode based on an adjustable structure to an adsorption-rapid degradation technology of oxygen-containing volatile organic matters difficult to degrade and patents and the like are not reported.
Disclosure of Invention
The invention aims to provide a carbon nanotube modified carbon cloth electrode with an adjustable structure and a preparation method and application thereof. The invention fully utilizes the physical adsorption and the electro-catalysis performance of the carbon nano tube modified carbon cloth electrode to realize the high-efficiency removal of the refractory oxygen-containing volatile organic compounds in the water phase industry.
Aiming at the above purposes, the technical scheme adopted by the invention is specifically as follows.
The invention provides an application of a carbon nanotube modified carbon cloth electrode with an adjustable structure in the aspects of adsorption-electrochemical oxidation treatment of refractory oxygen-containing volatile organic compounds, wherein the carbon nanotube modified carbon cloth electrode with the adjustable structure is prepared by the following steps:
(1) Pretreating the carbon cloth;
(2) Immersing the pretreated carbon cloth into an ethanol solution of a transition metal catalyst, performing ultrasonic treatment, and drying after immersion to obtain a catalyst-loaded carbon cloth;
(3) Injecting a precursor solution consisting of a carbon source and water into a vaporizer, vaporizing the precursor solution in the vaporizer, then feeding the vaporized precursor solution and carrier gas into a heating tube type furnace with a carbon cloth loaded with a catalyst in the central area, and growing carbon nanotubes in situ on the surface of the carbon cloth to obtain the carbon nanotube modified carbon cloth electrode.
In the invention, the oxygen-containing volatile organic compound difficult to degrade comprises one or more of methyl methacrylate, cyclohexanone, methyl tert-butyl ether, benzaldehyde and propyl acetate.
In the invention, a carbon cloth electrode modified by carbon nano tubes is used as an anode, a platinum sheet is used as a cathode, and Na is used 2 SO 4 The solution is used as a supporting electrolyte, the carbon nano tube modified carbon cloth electrode is firstly immersed into the solution of the oxygen-containing volatile organic compound which is difficult to degrade for adsorption and enrichment, and then the oxygen-containing volatile organic compound is electro-oxidatively degraded in a constant current mode.
In the invention, the initial concentration of the refractory oxygen-containing volatile organic compound is 10-500mg/L; the adsorption enrichment time is 10-30h, and the current density is 1-100mA/cm 2 The electrooxidation time is 10-200min. Preferably, the initial concentration of the refractory oxygen-containing volatile organic compound is 50-150mg/L; the adsorption enrichment time is 15-25h, and the current density is 10-50mA/cm 2 The electrooxidation time is 80-180min.
In the invention, in the step (1), the pretreatment method comprises the following steps: firstly, putting carbon cloth into acetone to be soaked for 1-4h, washing by deionized water and drying; then placing the mixture into a water bath at the temperature of 75-85 ℃ in a volume ratio of concentrated sulfuric acid to concentrated nitric acid of 3:1, condensing and refluxing for 2-8h; finally, washing the mixture to be neutral by deionized water, and drying the mixture for later use.
In the invention, in the step (2), the ultrasonic time is 20-60min, the dipping time is 6-24h, the transition metal catalyst is one or more of ferric nitrate, nickel nitrate or aluminum nitrate, and the concentration of the transition metal catalyst solution is 0.05-0.2mol/L.
In the invention, in the step (3), the carbon source is toluene, and the molar percentage content of water in the precursor solution is 1-20%. Preferably, the molar percentage of water in the precursor solution is between 5 and 15%. More preferably, the water content of the precursor solution is 10% by mole.
In the invention, in the step (3), the carrier gas is nitrogen, the flow rate of the carrier gas is 100-400ml/min, the heating rate of the tube furnace is 5-10 ℃/min, the precursor solution is injected into the vaporizer when the temperature of the tube furnace is raised to 500-700 ℃, the injection speed is 5-20 mu L/min, and the heat of the tube furnace is continuously preserved for 1-3h after the temperature is raised to 1000-1100 ℃.
The invention also provides a carbon nanotube modified carbon cloth electrode with an adjustable structure for the application.
The invention further provides a preparation method of the carbon nanotube modified carbon cloth electrode with the adjustable structure, which comprises the following steps:
(1) Pretreating the carbon cloth;
(2) Immersing the pretreated carbon cloth into an ethanol solution of a transition metal catalyst, performing ultrasonic treatment, and drying after immersion to obtain a catalyst-loaded carbon cloth;
(3) Injecting a precursor solution consisting of a carbon source and water into a vaporizer, vaporizing the precursor solution in the vaporizer, then feeding the vaporized precursor solution and carrier gas into a heating tube furnace provided with a carbon cloth loaded with a catalyst in the central area, and growing carbon nanotubes on the surface of the carbon cloth in situ to obtain the carbon nanotube modified carbon cloth electrode.
In the invention, in the step (3), when the carbon nano tube grows by chemical vapor deposition, the used equipment mainly comprises a micro injection pump, carrier gas, a gas flowmeter, a vaporizer and a tubular furnace, wherein the carrier gas is controlled by the gas flowmeter and enters the vaporizer by two paths together with the micro injection pump, and the vaporizer is connected with the tubular furnace. The tube furnace is a horizontal high-temperature tube furnace, a precursor solution of a carbon source and water is filled in the micro-injection pump, and the water is used as a growth promoter and a reducing agent; the vaporizer can stably vaporize the precursor solution, and the precursor solution and the carrier gas are mixed and distributed in the vaporizer to generate precursor gas with continuous and stable concentration and the precursor gas is introduced into the tube furnace.
In the invention, in the step (3), the carrier gas is nitrogen, and the influence factors can be adjusted as follows: the content of water is 1-20%, the flow rate of carrier gas is 100-400ml/min, the heating rate of the tube furnace is 5-10 ℃/min, the micro-injection pump is started to inject precursor solution when the temperature of the tube furnace is raised to 500-700 ℃, the speed of injecting the precursor solution by the micro-injection pump is 5-20 mu L/min, and the temperature of the high-temperature tube furnace is raised to 1000-1100 ℃, and then the temperature is kept for 1-3h.
Compared with the prior art, the invention has the advantages that,
(1) The carbon nanotube modified carbon cloth electrode adopts water as a reducing agent and a growth assistant, the reaction condition is mild, and the preparation method is simple.
(2) According to the research, the growth density and diameter of the carbon nano tube are adjusted through the concentration of the catalyst, the length of the carbon nano tube is adjusted and controlled through the reaction temperature, the reaction time, the nitrogen flow rate and the like, the density and the diameter of the carbon nano tube can be adjusted and controlled through the content of water, and functional groups and defects on the surface of the carbon nano tube can be influenced, so that the electrode adsorption and the electro-catalysis performance are promoted, different use requirements are met, and the application range of the material is expanded.
(3) The carbon nanotube modified carbon cloth electrode has strong adsorption performance and electrocatalysis performance. The carbon nanotube modified carbon cloth is used as an anode, the limitation of low oxygen evolution potential of the carbon electrode as an electrocatalytic anode is solved by adopting an adsorption-electrooxidation technology, the organic matters are quickly degraded by adsorbing, enriching and electrooxidating the organic pollutants to generate surface hydroxyl radicals, the degradation efficiency of the oxygen-containing volatile organic matters which are difficult to degrade in the industry is greatly promoted, and the carbon nanotube modified carbon cloth is an excellent electrode with industrial application prospect.
(4) The carbon nanotube modified carbon cloth electrode has the advantages of strong stability, stable operation and no secondary pollution, the electrode can be regenerated and used after adsorption-electrooxidation, and high adsorbability and electrocatalytic activity can be maintained after multiple cycles.
Drawings
FIG. 1 is a schematic diagram of a system for manufacturing a carbon nanotube modified carbon cloth electrode with a controllable structure according to the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) image of an anodic carbon cloth substrate prepared according to the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the carbon nanotube-modified carbon cloth electrode in example 2 of the present invention.
Fig. 4 is a perspective electron microscope (TEM) image of the carbon nanotube-modified carbon cloth electrode of example 2 of the present invention.
Fig. 5 is an X-ray diffraction (XRD) pattern of the carbon nanotube-modified carbon cloth electrode of example 2 of the present invention.
FIG. 6 is a graph of Cyclic Voltammogram (CV) for evaluating electrocatalytic performance in example 2 of the present invention.
FIG. 7 is an Electrochemical Impedance Spectroscopy (EIS) chart for evaluating the electrocatalytic performance in example 2 of the present invention.
FIG. 8 is a graph showing the effect of different initial concentrations of methyl methacrylate on the adsorption-electrooxidation effect of the electrode in example 2 according to the present invention.
FIG. 9 is a graph showing the effect of different current densities on the adsorption-electrooxidation of methyl methacrylate in example 2 of the present invention.
Fig. 10 is a graph showing the effect of the carbon nanotube-modified carbon cloth anode on stability in example 2 of the present invention.
FIG. 11 is a graph showing the comparative effects of the preparation electrode on methyl methacrylate adsorption and adsorption-electrooxidation evaluated in example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. The following description is given in conjunction with the accompanying drawings and specific embodiments, but the present invention is not limited to the following embodiments.
FIG. 1 is a schematic diagram of a system for preparing a carbon nanotube modified carbon cloth electrode with an adjustable structure, which comprises a micro-injection pump, a carrier gas, a gas flow meter, a vaporizer and a high-temperature tube furnace; the carrier gas is controlled by a gas flowmeter and enters the vaporizer in two paths with the micro-injection pump, and the vaporizer is connected with the high-temperature tube furnace. The high-temperature tube furnace is horizontal, and a precursor solution of a carbon source and a growth promoter/reducing agent is filled in the micro-injection pump; the vaporizer can stably vaporize the precursor solution, and the precursor solution and the carrier gas are mixed and distributed in the vaporizer to generate the precursor gas with continuous and stable concentration and then the precursor gas is introduced into the tube furnace.
In the embodiment, the carbon nanotube modified carbon cloth electrode with the adjustable structure is prepared and then used for adsorbing-electrochemically oxidizing refractory oxygen-containing volatile organic compounds, and the method specifically comprises the following steps:
(1) And (3) soaking the carbon cloth in acetone for 1-4h to remove dirt, washing with deionized water and drying. Keeping the temperature of a water bath kettle at 75-85 ℃, and placing the mixture in a concentrated sulfuric acid-concentrated nitric acid volume ratio of 3:1 for 2-8h. Washing with deionized water to neutrality, and oven drying;
(2) Immersing the pretreated carbon cloth into an ethanol solution of a transition metal catalyst, performing ultrasonic treatment, and drying after immersion to obtain a catalyst-loaded carbon cloth;
(3) Injecting a precursor solution consisting of a carbon source and water into a vaporizer, vaporizing the precursor solution in the vaporizer, then feeding the vaporized precursor solution and carrier gas into a heating tube type furnace with a carbon cloth loaded with a catalyst in the central area, and growing carbon nanotubes in situ on the surface of the carbon cloth to obtain the carbon nanotube modified carbon cloth electrode.
(4) Taking the carbon nanotube modified carbon cloth with the adjustable structure prepared in the step (3) as an anode, a platinum sheet as a cathode and Na 2 SO 4 As a supporting electrolyte, a carbon nano tube modified carbon cloth electrode is firstly immersed into an oxygen-containing volatile organic compound solution for adsorption and enrichment, and then organic pollutants which are difficult to degrade are subjected to electrooxidation in a constant current mode.
Example 1
Firstly, putting a carbon cloth (2 multiplied by 2 cm) into acetone for soaking and decontamination for 3h, washing with deionized water and drying, and then putting the carbon cloth into concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, condensing and refluxing for 6h at 80 ℃, washing to neutrality by deionized water, and drying for later use. And immersing the carbon cloth subjected to acid treatment in 0.1M ferric nitrate catalyst solution prepared by ethanol for 30min by ultrasonic treatment, and drying after 8h of immersion to obtain the catalyst-loaded carbon cloth. Placing carbon cloth loaded with a catalyst in a tube furnace, under the protection of 350ml/min nitrogen gas, starting a micro injection pump to inject precursor solution when a high-temperature tube furnace is heated to 700 ℃ at a speed of 5 ℃/min, heating the high-temperature tube furnace to 1100 ℃ at the highest temperature, maintaining the reaction time for 3h, wherein the precursor injection speed of the micro injection pump is 10 mu L/min, the molar percentage of water is 5% (calculated by the molar ratio of water to methylbenzene), and the prepared electrode is named as CNTs-CC-1.
The CNTs-CC-1 electrode prepared by the method is used as an anode (2 x 2cm), a platinum sheet (2 x 2cm) is used as a cathode, and 100mL of Na with the concentration of 0.05M is used as electrolyte 2 SO 4 Solution (pH = 7) initial concentration of methyl methacrylate was 100mg/L. The anode prepared by the method is firstly placed in a pollutant solution of a reactor for 24 hours to achieve adsorption balance, and then 1 is adopted0mA/cm 2 And (3) degrading by constant current of current density, wherein the reaction time is 150min, and the electrode distance is 1cm.
The adsorption-electrooxidation effect of the carbon nano tube modified anode on methyl methacrylate is inspected, the removal efficiency of the methyl methacrylate after 24 hours of adsorption is 38.99%, and the removal efficiency of the methyl methacrylate after 150 minutes of degradation is 70.45%.
Example 2
Firstly, putting a carbon cloth (2 multiplied by 2 cm) into acetone for soaking and decontamination for 3h, washing with deionized water and drying, and then putting the carbon cloth into concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, condensing and refluxing for 6h at 80 ℃, washing to neutrality by deionized water, and drying for later use. And immersing the carbon cloth subjected to acid treatment in 0.1M ferric nitrate catalyst solution prepared by ethanol for 30min by ultrasonic treatment, and drying after 8h of immersion to obtain the catalyst-loaded carbon cloth. Placing carbon cloth loaded with a catalyst in a tube furnace, starting a micro-injection pump to inject precursor solution when the high-temperature tube furnace is heated to 700 ℃ at the speed of 5 ℃/min under the protection of 350ml/min nitrogen gas, heating the high-temperature tube furnace to 1100 ℃ at the maximum, maintaining the reaction time for 3h, wherein the precursor injection speed of the micro-injection pump is 10 mu L/min, the molar percentage content of water is 10%, and the prepared electrode is named as CNTs-CC-2.
As can be seen from the SEM images of FIG. 2 and FIG. 3, the preparation method grows dense tubular CNTs on the surface of the smooth carbon cloth in situ, and the CNTs uniformly cover the surface of the carbon cloth; as can be seen from the TEM image of fig. 4, the preparation method prepared the carbon nanotubes with micron-sized length; as can be seen from the XRD pattern of fig. 5, the preparation method can detect that the characteristic diffraction peak of carbon is located at 26.26 °, corresponding to the (002) plane of CNT.
The prepared carbon nanotube modified carbon cloth CNTs-CC-2 and untreated carbon cloth CC were used as anodes (1 × 1cm), respectively, and measurement was performed in a three-electrode system using an electrochemical workstation, and a platinum electrode (2 × 2cm) and Ag/AgCl were used as an auxiliary electrode and a reference electrode, respectively. Cyclic Voltammetry (CV) at 0.5M Na 2 SO 4 At 50mVs in solution -1 The scanning rate of (2). As shown in fig. 6, both electrodes clearly show almost reversible redox peaks and show similar surface electrochemical behavior. The carbon nanotubes prepared in example 2The anode peak current value of the modified carbon cloth electrode CNTs-CC-2 is 0.0257A/cm 2 . The anode peak current value of the untreated carbon cloth CC was 0.0168A/cm 2 。
The prepared carbon nano tube modified carbon cloth CNTs-CC-2 and the untreated carbon cloth CC are respectively used as anodes, an electrochemical workstation is used for measurement in a three-electrode system, and a platinum electrode (2 x 2cm) and Ag/AgCl are respectively used as an auxiliary electrode and a reference electrode. Electrochemical Impedance Spectroscopy (EIS) at 0.5M Na 2 SO 4 The method is carried out in solution, the frequency sweep range is 100 KHz to 100 mHz, and a sine wave with 10 mV amplitude is additionally added. The carbon nanotube-modified carbon cloth electrode CNTs-CC-2 prepared in example 2 had an equivalent series resistance (Rs) of 2.35 Ω and a charge transfer resistance (Rct) of 2.41 Ω, as shown in fig. 7, by fitting an equivalent circuit model to EIS data. The untreated carbon cloth CC had an equivalent series resistance (Rs) of 3.02 Ω and a charge transfer resistance (Rct) of 2.93 Ω.
The carbon nanotube-modified carbon cloth CNTs-CC-2 prepared in example 2 was used as an anode (2 × 2cm), a platinum sheet (2 × 2cm) was used as a cathode, and 100mL of Na with a concentration of 0.05M was used as an electrolyte 2 SO 4 Solution (pH = 7) with initial concentrations of methyl methacrylate of 100, 150, 250mg/L, respectively. The anode prepared by the method is firstly placed in a pollutant solution in a reactor for 24 hours to achieve adsorption balance, and then 10mA/cm is adopted 2 And (3) degrading by constant current of current density for 120min, wherein the electrode distance is 1cm. As shown in FIG. 8, when the initial concentrations of methyl methacrylate are 100, 150 and 250mg/L, the adsorption-electro-oxidative degradation efficiency of CNTs-CC-2 on methyl methacrylate reaches 79.28%, 92.20% and 97.26% respectively in 150 min.
The carbon nanotube modified carbon cloth CNTs-CC-2 prepared in example 2 was used as an anode (2 × 2cm), a platinum sheet (2 × 2cm) was used as a cathode, and 100mL of 0.05M Na was used as an electrolyte 2 SO 4 Solution (pH = 7) initial concentration of methyl methacrylate was 250mg/L. The anode prepared by the method is placed in a pollutant solution of a reactor for 24 hours to achieve adsorption balance, and 10mA/cm, 30 mA/cm and 50mA/cm are respectively adopted 2 And (3) degrading by constant current of current density, wherein the reaction time is 120min, and the electrode distance is 1cm. When the current is flowing, as shown in FIG. 9The densities are respectively 10mA/cm, 30 mA/cm and 50mA/cm 2 In the process, the adsorption-electrooxidation degradation efficiency of CNTs-CC-2 to methyl methacrylate reaches 93.74%, 96.90% and 100% respectively in 120 min.
As shown in FIG. 10, the results of 13 times of adsorption-electrooxidation cycles of treatment of methyl methacrylate at initial concentrations of 100mg/L using the electrode prepared in example 2 show that the adsorption amount of methyl methacrylate by the prepared electrode is 2.2mg/cm 2 Above all, the degradation efficiency exceeds 85%, and the stability is excellent.
Example 3
Firstly, putting a carbon cloth (2 multiplied by 2 cm) into acetone for soaking and decontamination for 3h, washing with deionized water and drying, and then putting the carbon cloth into concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3:1, condensing and refluxing for 6h at 80 ℃, washing with deionized water to be neutral, and drying for later use. And immersing the carbon cloth subjected to acid treatment in 0.1M ferric nitrate catalyst solution prepared by ethanol for 30min by ultrasonic treatment, and drying after 8h of immersion to obtain the catalyst-loaded carbon cloth. Placing carbon cloth loaded with a catalyst in a tube furnace, starting a micro-injection pump to inject precursor solution when the high-temperature tube furnace is heated to 700 ℃ at the speed of 5 ℃/min under the protection of 350ml/min nitrogen gas, heating the high-temperature tube furnace to 1100 ℃ at the maximum, maintaining the reaction time for 3h, wherein the precursor injection speed of the micro-injection pump is 10 mu L/min, the molar percentage content of water vapor is 15%, and the prepared electrode is named as CNTs-CC-3.
The CNTs-CC-3 electrode prepared by the method is used as an anode (2 x 2cm), a platinum sheet (2 x 2cm) is used as a cathode, and 100mL of Na with the concentration of 0.05M is used as electrolyte 2 SO 4 Solution (pH = 7) initial concentration of methyl methacrylate was 100mg/L. The anode prepared by the method is firstly placed in a pollutant solution in a reactor for 24 hours to achieve adsorption balance, and then 10mA/cm is adopted 2 And (3) degrading by constant current of current density, wherein the reaction time is 150min, and the electrode distance is 1cm.
And (3) examining the adsorption-electrooxidation effect of the carbon nano tube modified anode on methyl methacrylate, wherein the removal efficiency of 24h of adsorption is 42.91%, and after 150min of degradation, the removal efficiency of methyl methacrylate is 78.30%.
Example 4
The carbon nanotube-modified carbon cloth CNTs-CC-2 and the untreated carbon cloth CC prepared in example 2 were used as an anode (2 × 2cm), a platinum sheet (2 × 2cm) was used as a cathode, and 100mL of Na having a concentration of 0.05M was used as an electrolyte 2 SO 4 Solution (pH = 7) with an initial concentration of methyl methacrylate of 100mg/L. Using 10mA/cm 2 And (3) degrading by constant current of current density, wherein the reaction time is 150min, and the electrode distance is 1cm. The electrode is compared with the effect graph of methyl methacrylate electrooxidation and adsorption-electrooxidation degradation.
As shown in fig. 11, after 150min, the electrooxidation degradation efficiency of CC on methyl methacrylate was 12.05%, and the adsorption-electrooxidation degradation efficiency was 73.09%; the electro-oxidative degradation efficiency of CNTs-CC-2 to methyl methacrylate is 18.48%. The adsorption-electrooxidation degradation efficiency is 79.28%.
Claims (10)
1. The application of the carbon nanotube modified carbon cloth electrode with the adjustable structure in the aspects of adsorption-electrochemical oxidation treatment of refractory oxygen-containing volatile organic compounds is characterized in that the carbon nanotube modified carbon cloth electrode with the adjustable structure is prepared by the following steps:
(1) Pretreating the carbon cloth;
(2) Immersing the pretreated carbon cloth into an ethanol solution of a transition metal catalyst, performing ultrasonic treatment, and drying after immersion to obtain a catalyst-loaded carbon cloth;
(3) Injecting a precursor solution consisting of a carbon source and water into a vaporizer, vaporizing the precursor solution in the vaporizer, then feeding the vaporized precursor solution and carrier gas into a heating tube furnace provided with a carbon cloth loaded with a catalyst in the central area, and growing carbon nanotubes on the surface of the carbon cloth in situ to obtain the carbon nanotube modified carbon cloth electrode.
2. The use of claim 1, wherein the refractory oxygen-containing volatile organic compound comprises one or more of methyl methacrylate, cyclohexanone, methyl tert-butyl ether, benzaldehyde, and propyl acetate.
3. Use according to claim 1, characterized in thatThen, a carbon cloth electrode modified by carbon nano tubes is used as an anode, a platinum sheet is used as a cathode, and Na is used 2 SO 4 The solution is used as a supporting electrolyte, the carbon nano tube modified carbon cloth electrode is firstly immersed into the solution of the oxygen-containing volatile organic compound which is difficult to degrade for adsorption and enrichment, and then the oxygen-containing volatile organic compound is electro-oxidatively degraded in a constant current mode.
4. The use of claim 3, wherein the initial concentration of refractory oxygen-containing volatile organic compounds is 10-500mg/L; the adsorption enrichment time is 10-30h, and the current density is 1-100mA/cm 2 The electrooxidation time is 10-200min.
5. The use according to claim 1, wherein in step (1), the pre-treatment method comprises: firstly, putting carbon cloth into acetone to be soaked for 1-4h, washing by deionized water and drying; then placing the mixture into a water bath at the temperature of 75-85 ℃, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1, condensing and refluxing the mixed solution for 2-8h; and finally, washing the mixture to be neutral by using deionized water, and drying the mixture for later use.
6. The use of claim 1, wherein in the step (2), the ultrasonic time is 20-60min, the dipping time is 6-24h, the transition metal catalyst is one or more of ferric nitrate, nickel nitrate or aluminum nitrate, and the concentration of the transition metal catalyst solution is 0.05-0.2mol/L.
7. The use according to claim 1, wherein in step (3), the carbon source is toluene, and the water content in the precursor solution is 1-20 mol%.
8. The use according to claim 1, wherein in step (3), the carrier gas is nitrogen, the carrier gas flow is 100-400ml/min, the temperature rise rate of the tube furnace is 5-10 ℃/min, the precursor solution is injected into the vaporizer when the tube furnace is heated to 500-700 ℃, the injection rate is 5-20 μ L/min, and the temperature of the tube furnace is increased to 1000-1100 ℃, and then the heat preservation is continued for 1-3h.
9. A carbon nanotube modified carbon cloth electrode with a controllable structure for use according to any one of claims 1 to 8.
10. The method for preparing the carbon nanotube modified carbon cloth electrode with the controllable structure according to claim 9, comprising the following steps:
(1) Pretreating the carbon cloth;
(2) Immersing the pretreated carbon cloth into an ethanol solution of a transition metal catalyst, performing ultrasonic treatment, and drying after immersion to obtain a catalyst-loaded carbon cloth;
(3) Injecting a precursor solution consisting of a carbon source and water into a vaporizer, vaporizing the precursor solution in the vaporizer, then feeding the vaporized precursor solution and carrier gas into a heating tube furnace provided with a carbon cloth loaded with a catalyst in the central area, and growing carbon nanotubes on the surface of the carbon cloth in situ to obtain the carbon nanotube modified carbon cloth electrode.
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| CN117913301A (en) * | 2024-03-18 | 2024-04-19 | 中海储能科技(北京)有限公司 | Method for modifying battery carbon cloth electrode by metal carbide nano material |
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