CN114892201A - Phosphorus-doped porous carbon-coated graphite felt material and preparation method and application thereof - Google Patents

Phosphorus-doped porous carbon-coated graphite felt material and preparation method and application thereof Download PDF

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CN114892201A
CN114892201A CN202210512639.2A CN202210512639A CN114892201A CN 114892201 A CN114892201 A CN 114892201A CN 202210512639 A CN202210512639 A CN 202210512639A CN 114892201 A CN114892201 A CN 114892201A
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graphite felt
phosphorus
porous carbon
doped porous
parabens
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郭慢丽
沈佳
朱亚婷
宋璐洲
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South China Normal University
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    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a phosphorus-doped porous carbon-coated graphite felt material which comprises a graphite felt and a phosphorus-doped porous carbon material, wherein the graphite felt is a carbon substrate material, and the phosphorus-doped porous carbon is a modification material and is coated on the surface of carbon fibers of the graphite felt. The material is prepared by the following steps: s1: pretreating an original graphite felt material; s2: ultrasonic infiltration treatment: immersing the pretreated graphite felt into a phytic acid aqueous solution, drying for 8-24 hours at 70-70 ℃ after 15-60 min; s3:high-temperature carbonization treatment: and transferring the graphite felt into an atmosphere tube furnace for carbonization treatment, calcining for 0.5-1 h at the temperature rise rate of 5 ℃ per minute at 700-700 ℃ under the protection of nitrogen, and washing and drying the graphite felt after the tube furnace is cooled to the room temperature to obtain the phosphorus-doped porous carbon coated graphite felt material. The material is used as an electro-Fenton cathode and can electro-catalyze O 2 Reduction to form H 2 O 2 And the generated OH oxidizes the target pollutant to realize the complete degradation of the parabens pollutant in the water.

Description

Phosphorus-doped porous carbon-coated graphite felt material and preparation method and application thereof
Technical Field
The invention belongs to the field of organic pollutant removal, and particularly relates to a phosphorus-doped porous carbon-coated graphite felt material, a preparation method thereof and application thereof in degradation of parabens pollutants by electro-Fenton.
Background
With the rapid development of social economy, in recent years, water pollution has the characteristics of wide distribution range, diversified pollution sources and diversified pollutants in the global range. However, water resources are self-heating resources on which human beings live, and the problem of environmental water pollution which is becoming serious needs to be solved urgently. Pollutants are removed from water, the utilization rate of water resources is improved, water pollution is reduced, and the method becomes a hot spot concerned by people all over the world.
Among various pollutant removal methods, the physical method is simple and quick, but the incomplete degradation of the pollutants can cause secondary pollution to the environment; the biological method has the characteristics of good selectivity, safety and stability, but has long culture period for microorganisms, and is not beneficial to treating various emerging pollutants. The electro-Fenton oxidation method is a novel pollutant removal technology for degrading organic matters by utilizing strong oxidizing radicals, and has the obvious advantages of high degradation efficiency, good mineralization effect and no secondary pollution for organic matters difficult to remove. This method is to subject O to 2e process 2 Reduction to H 2 O 2 Reuse of Fe 2+ And H 2 O 2 OH generated by the reaction can completely degrade the target pollutants, and Fe generated by electrochemical reduction can be used 3+ Reduction to Fe 2+ . In the electro-Fenton technique, OH determines the rate of contaminant degradation, while the electrode material influences H 2 O 2 The yield of (2). Therefore, the choice of cathode material is critical to the electro-fenton process.
O 2 +2e - +2H + ＝H 2 O 2 (eq.1)
Fe 2+ +H 2 O 2 ＝Fe 3+ +·OH+OH - (eq.2)
Fe 3+ +e - ＝Fe 2+ (eq.3)
The graphite felt is a three-dimensional self-supporting carbon material consisting of carbon fibers, has the advantages of loose internal structure, large void passage, low cost, no toxicity, corrosion resistance, good mechanical properties and the like, is usually used as an electrode material and is applied to the fields of batteries, supercapacitors, electrochemical catalysis, advanced oxidation technologies and the like. However, the graphite felt has poor wettability to an electrolyte solution, the surface of the carbon fiber is too smooth to be beneficial to electrochemical reaction, and the graphite felt is usually required to be modified when being applied to an electro-Fenton process so as to improve the degradation efficiency of the graphite felt to target pollutants.
Phytic acid is a natural compound rich in phosphate. As the main existing form of phosphorus element in seeds, phytic acid accounts for 60% -70% of total phosphorus in grains, oil seeds and nuts, so that the phytic acid has an important role in the germination process of the seeds.
The parabens are organic matters with parabens as main structures, and the main structural formula of the parabens is as follows:
Figure BDA0003640040900000021
because of the characteristics of low cost, wide application range, good antibacterial effect and the like, the nipagin ester substances become preservatives for tens of thousands of cosmetics and partial foods. The use of the paraben preservatives in large quantities leads to residues in environmental water, soil and sediments. However, excessive use of such preservatives can not only adversely affect the skin, endocrine system and reproductive system of the human body, but also threaten the stability of microbial communities in water, and is not beneficial to the development of aquatic ecosystems. Therefore, it is necessary to remove the parabens in the environment by a highly efficient, clean, safe and stable technique.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a phosphorus-doped porous carbon-coated graphite felt material, which has good hydrophilicity and electrochemical catalytic activity.
In order to realize the aim, the invention provides a preparation method of a phosphorus-doped porous carbon-coated graphite felt material, which comprises the following steps:
s1: pretreating an original graphite felt material to remove surface impurities of the original graphite felt material;
s2: ultrasonic infiltration treatment: immersing the pretreated graphite felt into a phytic acid aqueous solution, drying for 8-24 hours at 70-70 ℃ after 15-60 min;
s3: high-temperature carbonization treatment: and (4) transferring the graphite felt obtained in the step (S2) into an atmosphere tube furnace for carbonization, calcining for 0.5-1 h at the temperature rising rate of 5 ℃ per minute at 700-700 ℃ under the protection of nitrogen, and washing and drying the obtained graphite felt after the tube furnace is cooled to the room temperature to obtain the phosphorus-doped porous carbon coated graphite felt material.
Compared with the prior art, the phytic acid is used as a phosphorus source to dope the graphite felt, and after high-temperature carbonization, the phytic acid can generate a remarkable nano-scale pore structure and a 3D pore channel with mass transfer advantages, so that the specific surface area is enlarged, and the C-P bond can provide an active site for electrochemical reaction, thereby improving the electrochemical activity of the graphite felt. The phosphorus-doped porous carbon-coated graphite felt material prepared by the preparation method can be used for electrocatalysis of O 2 Reduction to form H 2 O 2 And the generated OH oxidizes the target pollutant to realize the complete degradation of the parabens pollutant in the water.
Preferably, in step S2, the phytic acid in the phytic acid aqueous solution is 2.1% to 6.3% by weight.
Preferably, in step S1, the raw graphite felt material is pre-treated by the following steps: respectively carrying out ultrasonic pretreatment on an original graphite felt material in ethanol and deionized water for 0.25-1.5 h to remove impurities attached to the surface of the graphite felt, and then drying at 70-70 ℃ for 8-24 h.
Preferably, in step S3, the carbonized graphite felt is washed and dried by the following steps: ultrasonically washing the obtained graphite felt for 1-6 times by using ethanol, ultrasonically washing the graphite felt for 4-8 times by using ultrapure water, wherein each time lasts for 10-60 min, and then drying the graphite felt for 8-24 h at 70-70 ℃.
The invention also provides a phosphorus-doped porous carbon-coated graphite felt material prepared by the preparation method, which comprises a graphite felt and a phosphorus-doped porous carbon material, wherein the graphite felt is a carbon substrate material, and the phosphorus-doped porous carbon is a modification material and is coated on the surface of carbon fibers of the graphite felt. The phosphorus-doped porous carbon-coated graphite felt material can be used for electrocatalysis of O 2 Reduction to form H 2 O 2 And the generated OH oxidizes the target pollutant to realize the complete degradation of the parabens pollutant in the water.
The invention also provides application of the phosphorus-doped porous carbon-coated graphite felt material as an electro-Fenton cathode in degrading nipagin ester pollutants in water. The phosphorus-doped porous carbon-coated graphite felt material has efficient and stable degradation capability on the nipagin ester pollutants as the electro-Fenton cathode.
The invention also provides a method for degrading parabens pollutants in water by electro-Fenton based on the phosphorus-doped porous carbon-coated graphite felt material, which comprises the following steps:
s1: the phosphorus-doped porous carbon-coated graphite felt material is used as an electro-Fenton cathode material and is cut into 1 multiplied by 1cm 2 Size at 1X 1cm 2 Is 2 x 2cm by using GF or P-GF as working electrode 2 The platinum mesh electrode is a counter electrode, and is arranged in parallel with the working electrode at an interval of 1 cm; taking a saturated calomel electrode as a reference electrode;
s2: using H 2 SO 4 0.05 mol.L -1 Na of (2) 2 SO 4 The initial pH of the electrolyte solution is adjusted to 3.0-6.0, and the electrolyte solution contains 0.00-2.0 mmol.L -1 Fe 2+ And a target contaminant of the paraben class, O being introduced before degradation 2 At 0.6 L.min -1 At a rate of 30 minutes into the solution, O during the degradation process 2 At 0.6 L.min -1 The rate of (2) is introduced into a reactor, electro-Fenton degradation is carried out at a constant potential of 0.0 to (-0.6) V, 0.2mL of samples are taken at intervals of 30min, and the target pollutants are quantified by adopting a high performance liquid chromatography after filtration.
Further, in step S2, the target contaminants of parabens are one or more of methylparaben, ethylparaben, propylparaben, and butylparaben.
Preferably, in step S2, when the electrolyte solution contains only one target pollutant of the paraben, the target pollutant is quantified by using an isocratic elution method: the mobile phase is methanol, water and acetic acid with a volume ratio of 50:50:0.1, and the flow rate is 1 mL/min -1 The MePa concentration was measured at 254nm using HPLC equipped with a UV-vis detector at 35 ℃ and a sample size of 20. mu.L using a C18 column.
Preferably, in step S2, when the electrolyte solution contains a plurality of target contaminants of the parabens, the target contaminants of the parabens are simultaneously quantified by using a gradient elution method: the mobile phase is water and methanol, the volume percentages of methanol at 0.0min, 10.0min and 17.0min in the mobile phase are respectively 60%, 65% and 67.8%, and the flow rate is 0.8 mL/min -1 The concentration of various target contaminants of the parabens was determined simultaneously by HPLC at 254nm using a column temperature of 35 ℃ and a sample size of 20 μ L using a C18 column.
The invention aims at the pollution problem of the nipagin ester in the environmental water, combines the hot spot field of pollutant degradation and carbon material at home and abroad at present, constructs a preparation method of a phosphorus-doped porous carbon-coated graphite felt material, takes the material as an electro-Fenton cathode and can electro-catalyze O 2 Reduction to form H 2 O 2 And the generated OH oxidizes the target pollutant to realize the complete degradation of the parabens pollutant in the water.
Drawings
Fig. 1 is a schematic view of a process for preparing a phosphorus-doped porous carbon-coated graphite felt material.
Fig. 2 is SEM images of cathode materials manufactured by different examples and comparative examples, wherein, fig. (a1) and (a2) are SEM images of cathode materials manufactured by comparative examples; FIGS. (b1) and (b2) are SEM images of the cathode material prepared in example 1; FIGS. (c1) and (c2) are SEM images of the cathode material prepared in example 2; fig. (d1) and (d2) are SEM images of the cathode material prepared in example 3.
FIG. 3 is a pore size distribution curve of the cathode material (P-GF-2) prepared in example 2.
FIG. 4 is a graph comparing the effect of degrading MePa of the cathode materials prepared in different examples and comparative examples.
FIG. 5 shows different Fe 2+ Graph comparing the effect of concentration on the degradation effect of the cathode material (P-GF-2) prepared in example 2 on MePa electro-Fenton degradation.
FIG. 6 is a graph comparing the effect of different applied potentials on the degradation effect of the cathode material (P-GF-2) prepared in example 2 on MePa electro-Fenton degradation.
FIG. 7 is a graph comparing the effect of different initial pH values on the MePa electro-Fenton degradation effect of the cathode material (P-GF-2) prepared in example 2.
FIG. 8 is a graph of the simultaneous electro-Fenton degradation time of the cathode material (P-GF-2) prepared in example 2 for MePa, EtPa, PrPa and BuPa.
FIG. 9 is a graph showing the reusability of the cathode material (P-GF-2) prepared in example 2 to MePa electro-Fenton degradation.
FIG. 10 is an EPR spectrum of an electro-Fenton cathode using the cathode material (P-GF-2) obtained in example 2.
Detailed Description
The present invention is further illustrated by the following examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations or modifications made based on the present invention are intended to be within the scope of the present invention.
Example 1:
referring to fig. 1, the present embodiment prepares the phosphorus-doped porous carbon-coated graphite felt material according to the following steps:
s1: pretreating the original graphite felt material, and cutting the original graphite felt into 3 x 4cm 2 Respectively carrying out ultrasonic pretreatment for 1h in ethanol and deionized water to remove the surface attachments of the graphite feltThe impurities are then dried at 80 ℃ for 12 h.
S2: ultrasonic infiltration treatment: immersing the pretreated graphite felt into 50mL of 2.1% phytic acid-containing aqueous solution, carrying out ultrasonic treatment for 45min, and drying at 80 ℃ for 12 h.
S3: high-temperature carbonization treatment: and (4) transferring the graphite felt obtained in the step (S2) into an atmosphere tube furnace for carbonization, calcining for 1h at 800 ℃ at a heating rate of 5 ℃ per minute under the protection of nitrogen, after the tube furnace is cooled to room temperature, ultrasonically washing the obtained graphite felt for 2 times by using ethanol, ultrasonically washing for 6 times by using ultrapure water for 30 minutes each time, and then drying for 12h at 80 ℃. Marking the obtained phosphorus-doped porous carbon-coated graphite felt material as P-GF-1.
Example 2:
in this example, a phosphorus-doped porous carbon-coated graphite felt material was prepared by the following steps:
s1: pretreating the original graphite felt material, and cutting the original graphite felt into 3 x 4cm 2 Respectively carrying out ultrasonic pretreatment in ethanol and deionized water for 1h to remove impurities attached to the surface of the graphite felt, and then drying at 80 ℃ for 12 h.
S2: ultrasonic infiltration treatment: immersing the pretreated graphite felt into 50mL of aqueous solution containing 4.2% of phytic acid, carrying out ultrasonic treatment for 45min, and drying at 80 ℃ for 12 h.
S3: high-temperature carbonization treatment: and (4) transferring the graphite felt obtained in the step (S2) into an atmosphere tube furnace for carbonization, calcining for 1h at 800 ℃ at a heating rate of 5 ℃ per minute under the protection of nitrogen, after the tube furnace is cooled to room temperature, ultrasonically washing the obtained graphite felt for 2 times by using ethanol, ultrasonically washing for 6 times by using ultrapure water for 30 minutes each time, and then drying for 12h at 80 ℃. The obtained phosphorus-doped porous carbon-coated graphite felt material is marked as P-GF-2.
Example 3:
in this example, a phosphorus-doped porous carbon-coated graphite felt material was prepared by the following steps:
s1: pretreating the original graphite felt material, and cutting the original graphite felt into 3 x 4cm 2 Respectively carrying out ultrasonic pretreatment on the small blocks in ethanol and deionized water for 1 hour to removeRemoving impurities attached to the surface of the graphite felt, and drying at 80 ℃ for 12 hours.
S2: ultrasonic infiltration treatment: immersing the pretreated graphite felt into 50mL of aqueous solution containing 6.3% of phytic acid, carrying out ultrasonic treatment for 45min, and drying at 80 ℃ for 12 h.
S3: high-temperature carbonization treatment: and (4) transferring the graphite felt obtained in the step (S2) into an atmosphere tube furnace for carbonization, calcining for 1h at 800 ℃ at a heating rate of 5 ℃ per minute under the protection of nitrogen, after the tube furnace is cooled to room temperature, ultrasonically washing the obtained graphite felt for 2 times by using ethanol, ultrasonically washing for 6 times by using ultrapure water for 30 minutes each time, and then drying for 12h at 80 ℃. Marking the obtained phosphorus-doped porous carbon-coated graphite felt material as P-GF-3.
Comparative example:
this example prepares a graphite felt material by the following steps:
s1: pretreating the original graphite felt material, and cutting the original graphite felt into 3 x 4cm 2 Respectively carrying out ultrasonic pretreatment in ethanol and deionized water for 1h to remove impurities attached to the surface of the graphite felt, and then drying at 80 ℃ for 12 h.
S2: ultrasonic infiltration treatment: the pretreated graphite felt is immersed in 50mL of ultrapure water, is subjected to ultrasonic treatment for 45min and is dried at 80 ℃ for 12 h.
S3: high-temperature carbonization treatment: and (4) transferring the graphite felt obtained in the step (S2) into an atmosphere tube furnace for carbonization, calcining for 1h at 800 ℃ at a heating rate of 5 ℃ per minute under the protection of nitrogen, after the tube furnace is cooled to room temperature, ultrasonically washing the obtained graphite felt for 2 times by using ethanol, ultrasonically washing for 6 times by using ultrapure water for 30 minutes each time, and then drying for 12h at 80 ℃. The resulting material was labeled GF.
The morphology of the cathode materials prepared in examples 1-3 and comparative example is shown in FIG. 2. As can be seen from fig. (a1) and (a2), the comparative example still retained intact carbon fibers and a smooth surface. And after the material is soaked in phytic acid aqueous solution and then is treated at high temperature, the surface of the material can have attachments wrapping carbon fibers, so that the roughness of the surface of the fibers is increased. As shown in FIGS. b1 and b2, the cathode material (P-GF-1) obtained in example 1 had a dense film-like material on the surface; as shown in (c1) and (c2), the attachment on the cathode material (P-GF-2) prepared in example 2 exhibited a large number of nanopore structures; as shown in the graphs (d1) and (d2), the area covered by the deposit on the cathode material (P-GF-3) prepared in example 3 further increased.
Comparison with the material prepared in comparative example (0.17 m) 2 ·g -1 ) In contrast, the surface area (17.1 m) of the cathode material (P-GF-2) prepared in example 2 2 ·g -1 ) The improvement is remarkable. As shown in FIG. 3, the pore size distribution of the cathode material (P-GF-2) prepared in example 2 was centered at 2.7 nm. The existence of these mesoporous structures in the cathode material (P-GF-2) prepared in example 2 greatly expands the specific surface area of the material, bringing more active reaction sites, and thus enhancing the electrochemical catalytic ability as a cathode material.
Application example 1: application of phosphorus-doped porous carbon-coated graphite felt material in electro-Fenton degradation of MePa (methyl paraben)
The reaction device of the electro-Fenton experiment mainly comprises a traditional three-electrode system and a soft rubber tube for introducing oxygen. The cathode materials prepared in examples 1 to 3 and comparative example were uniformly cut into 1X 1cm 2 Respectively as a working electrode, a platinum mesh electrode (2X 2 cm) 2 ) The counter electrode was spaced 1cm from the working electrode and placed in parallel. A Saturated Calomel Electrode (SCE) was used as a reference electrode. The degradation experiment of this example contained 10 mg. L in 40mL -1 MePa and 0.50 mmol. L -1 Fe 2+ 0.05 mol. L of oxygen saturation of -1 Na 2 SO 4 In solution, under the condition of applying constant-0.4V potential. Using H 2 SO 4 The initial pH of the solution was adjusted to 3.0 to ensure that the reaction was under optimal conditions for electro-fenton. To ensure O in the solution at the beginning of the experiment 2 Saturation is reached and O is added before degradation 2 At 0.6 L.min -1 At a rate of 30 minutes into the solution, O during the degradation process 2 At 0.6 L.min -1 Is introduced into the reactor at the rate of (2) and the degradation time is 3 h. 0.2mL of the sample was sampled every 30 minutes, and the concentration of MePa was measured by high performance liquid chromatography after filtration.
Specifically, isocratic elution is adoptedThe method of (1) measures the concentration of MePa: the mobile phase comprises methanol, water and acetic acid at a volume ratio of 50:50:0.1, and the flow rate is 1 mL/min -1 The MePa concentration was measured at a wavelength of 254nm by HPLC using a UV-vis detector at a column temperature of 35 ℃ and a sample volume of 20. mu.L, and the elution peak of MePa was around 6min by using a C18 column.
The degradation result is shown in figure 4, and within 3h, the degradation rates of GF and P-GF-2 materials to MePa are respectively 50.5% and 77.7%; the P-GF-2 material showed the best degradation, i.e. example 2 was the best example.
Optimization experimental example: fe in electrolyte solution 2+ Optimisation of concentration
Referring to application example 1, P-GF-2 prepared in example 2 is used as a cathode material, other parameters are unchanged, and Fe is controlled 2+ The concentrations are 0.00, 0.25, 0.50, 1.0 and 2.0 mmol.L respectively -1 MePa was degraded, and as shown in FIG. 5, the degradation result showed Fe 2+ The concentration is 1.0 mmol.L -1 The degradation effect is optimal.
Optimization experimental example: optimization of applied potential
Referring to application example 1, P-GF-2 prepared in example 2 is used as a cathode material, other parameters are unchanged, and Fe is controlled 2+ The concentration is 1.0 mmol.L -1 And controlling the applied potential to be 0.0, -0.2, -0.4, -0.6V and the non-applied potential respectively to degrade the MePa. As shown in FIG. 6, the results showed that the results were similar between-0.4V and-0.6V, and-0.4V was selected as the optimum applied potential in view of reducing the power consumption.
Optimization experimental example: optimization of pH
Reference application example 1, P-GF-2 prepared in example 2 was used as a cathode material to control Fe 2+ The concentration is 1.0 mmol.L -1 The initial pH was 3.0, 4.0, 5.0 and 6.0, respectively, to degrade MePa, as shown in fig. 7, showing that the degradation effect was the best at pH 3.0.
Application example 2: application of phosphorus-doped porous carbon-coated graphite felt material to simultaneous electro-Fenton degradation of four kinds of nipagin ester pollutants
Reference application example 1, with P-GF-2 obtained in example 2 as the anionControl of Fe with constant other parameters 2+ The concentration is 1.0 mmol.L -1 The electrolyte solution contains four kinds of paraben pollutants of MePa (methyl paraben), EtPa (ethyl paraben), PrPa (propyl paraben) and BuPa (butyl paraben) at the same time, and the initial concentration of the four kinds of paraben pollutants is 10 mg.L -1 And determining the concentrations of the four kinds of paraben pollutants by adopting high performance liquid chromatography. Simultaneously quantifying a plurality of target pollutants of the parabens by adopting a gradient elution method: the mobile phase is a mixed solution of water (A) and methanol (B), and the flow rate is 0.8 mL/min -1 The volume percentages of mobile phase B at 0.0min, 10.0min and 17.0min were 60%, 65% and 67.8%, respectively. The concentrations of the target contaminants of various parabens were determined simultaneously by HPLC at 254nm with a column temperature of 35 ℃ and a sample size of 20. mu.L using a C18 column with elution peaks near 5, 7, 10, 15min for MePa, EtPa, PrPa and BuPa, respectively.
The degradation results are shown in FIG. 8, and the degradation rates of the P-GF-2 material to MePa, EtPa, PrPa and BuPa are 88.7%, 72.5%, 77.4% and 100% within 5 h.
Application example 3: application of phosphorus-doped porous carbon-coated graphite felt material to electro-Fenton degradation of multiple MePa
Referring to application example 1, P-GF-2 prepared in example 2 is used as a cathode material, other parameters are unchanged, and Fe is controlled 2+ The concentration is 1.0 mmol.L -1 And directly and repeatedly using the phosphorus-doped porous carbon-coated graphite felt material P-GF-2 for electro-Fenton degradation of MePa. As shown in fig. 7, after seven repetitions, the degradation rate of MePa still reached 77.1%. Therefore, the phosphorus-doped porous carbon-coated graphite felt material prepared by the invention has good reusability.
Test example: detection of free radicals of phosphorus-doped porous carbon-coated graphite felt material in electro-Fenton process
Referring to application example 1, P-GF-2 prepared in example 2 is used as a cathode material, other parameters are unchanged, MePa is not contained in an electrolyte solution, and Fe is controlled 2+ The concentration is 1.0 mmol.L -1 DMPO concentration of 10 mmol. L -1 Continuously introducing oxygen and applying potential, after 5minAfter 1mL of the solution was filtered through a 0.22 μm filter, the type of the radical contained in the system was measured by an electron paramagnetic resonance spectrometer (EPR).
As shown in FIG. 10, there is a distinct 1:2:2:1 quadruple signal peak in the EPR spectrum, which is a characteristic peak of DMPO/. OH complex, confirming that in the above application examples, OH is indeed generated by electro-Fenton reaction, and the contaminant is completely degraded by OH.
Compared with the prior art, the invention provides an organic pollutant degradation system taking a phosphorus-doped porous carbon material coated graphite felt material as an electro-Fenton cathode material. The cathode material is prepared by forming a layer of phosphorus-doped porous carbon on the surface of graphite felt carbon fiber by phytic acid through a high-temperature solid phase method. With the doping of phosphorus and the introduction of a large number of carbon porous structures, the hydrophilicity and the electrochemical catalytic activity of the graphite felt material coated with the phosphorus-doped porous carbon material are remarkably improved. The result shows that the phosphorus-doped porous carbon material coated graphite felt cathode material has high-efficiency degradation capability on methyl paraben and universality on removal of methyl paraben under constant potential. Meanwhile, the graphite felt material coated with the phosphorus-doped porous carbon material has excellent reusability, so that the graphite felt material becomes a general cathode material with great potential application value, and PPCPs pollutants can be efficiently and stably degraded by the electro-Fenton technology.
The invention is not limited to the use as described and illustrated embodiments, which are fully applicable to a variety of fields of application, and further modifications and variations readily will occur to those skilled in the art without departing from the spirit and scope of the invention, and it is intended that all such modifications and variations be considered as within the scope of the invention as hereinafter claimed.
The above description is only a few examples of the present invention, and does not limit the scope of the present invention, and it should be appreciated by those skilled in the art that the equivalent alternatives and obvious variations of the present invention are included in the scope of the present invention.

Claims (10)

1. A preparation method of a phosphorus-doped porous carbon-coated graphite felt material is characterized by comprising the following steps: the method comprises the following steps:
s1: pretreating an original graphite felt material to remove surface impurities of the original graphite felt material;
s2: ultrasonic infiltration treatment: immersing the pretreated graphite felt into a phytic acid aqueous solution, drying for 8-24 hours at 70-70 ℃ after 15-60 min;
s3: high-temperature carbonization treatment: and (4) transferring the graphite felt obtained in the step (S2) into an atmosphere tube furnace for carbonization, calcining for 0.5-1 h at the temperature rising rate of 5 ℃ per minute at 700-700 ℃ under the protection of nitrogen, and washing and drying the obtained graphite felt after the tube furnace is cooled to the room temperature to obtain the phosphorus-doped porous carbon coated graphite felt material.
2. The method of claim 1, wherein: in step S2, the phytic acid in the phytic acid aqueous solution is 2.1% to 6.3% by mass.
3. The method of claim 1, wherein: in step S1, the raw graphite felt material is pre-treated by the following steps: respectively carrying out ultrasonic pretreatment on an original graphite felt material in ethanol and deionized water for 0.25-1.5 h to remove impurities attached to the surface of the graphite felt, and then drying at 70-70 ℃ for 8-24 h.
4. The method of claim 1, wherein: in step S3, the carbonized graphite felt is washed and dried by the following steps: ultrasonically washing the obtained graphite felt for 1-6 times by using ethanol, ultrasonically washing the graphite felt for 4-8 times by using ultrapure water, wherein each time lasts for 10-60 min, and then drying the graphite felt for 8-24 h at 70-70 ℃.
5. A phosphorus-doped porous carbon-coated graphite felt material is characterized in that: the carbon fiber composite material comprises a graphite felt and a phosphorus-doped porous carbon material, wherein the graphite felt is a carbon substrate material, and the phosphorus-doped porous carbon is a modification material and is coated on the surface of carbon fiber of the graphite felt; the phosphorus-doped porous carbon-coated graphite felt material is prepared by the preparation method according to any one of claims 1 to 4.
6. The application of the phosphorus-doped porous carbon-coated graphite felt material as claimed in claim 5 as an electro-Fenton cathode in degrading parabens pollutants in water.
7. A method for degrading parabens pollutants in water by electro-Fenton based on a phosphorus-doped porous carbon-coated graphite felt material is characterized by comprising the following steps: the method comprises the following steps:
s1: the phosphorus-doped porous carbon-coated graphite felt material according to claim 5 is used as an electro-Fenton cathode material and is cut to 1 x 1cm 2 The size of the electrode is 2X 2cm 2 The platinum mesh electrode is a counter electrode, and is arranged in parallel with the working electrode at an interval of 1 cm; taking a saturated calomel electrode as a reference electrode;
s2: using H 2 SO 4 0.05 mol/L -1 Na (b) of 2 SO 4 The initial pH of the electrolyte solution is adjusted to 3.0-6.0, and the electrolyte solution contains 0.00-2.0 mmol.L -1 Fe 2+ And a target contaminant of the paraben class, O being introduced before degradation 2 At 0.6 L.min -1 At a rate of 30 minutes into the solution, O during the degradation process 2 At 0.6 L.min -1 The sample is introduced into a reactor at the speed of (2) and subjected to electro-Fenton degradation at a constant potential of (0.0) (-0.6) V, 0.2mL of the sample is sampled at intervals of 30min, and the target pollutant is quantified by high performance liquid chromatography after filtration.
8. The method of electro-Fenton degradation of parabens in water of claim 7, wherein: in step S2, the target contaminants of parabens are one or more of methylparaben, ethylparaben, propylparaben, and butylparaben.
9. The electro-Fenton degradation of parabens in water according to claim 8The method of (2), characterized by: in step S2, when the electrolyte solution contains only one target pollutant of parabens, the target pollutant is quantified by isocratic elution: the mobile phase is methanol, water and acetic acid with a volume ratio of 50:50:0.1, and the flow rate is 1 mL/min -1 The MePa concentration was measured at 254nm using HPLC equipped with a UV-vis detector at 35 ℃ and a sample size of 20. mu.L using a C18 column.
10. The method of electro-Fenton degradation of parabens in water of claim 8, wherein: in step S2, when the electrolyte solution contains multiple kinds of targeted contaminants of parabens, the targeted contaminants of the parabens are quantified simultaneously by a gradient elution method: the mobile phase is water and methanol, the volume percentages of methanol at 0.0min, 10.0min and 17.0min in the mobile phase are respectively 60%, 65% and 67.8%, and the flow rate is 0.8 mL/min -1 The concentration of various target contaminants of the parabens was determined simultaneously by HPLC at 254nm using a column temperature of 35 ℃ and a sample size of 20 μ L using a C18 column.
CN202210512639.2A 2022-05-12 2022-05-12 Phosphorus-doped porous carbon-coated graphite felt material and preparation method and application thereof Pending CN114892201A (en)

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