CN115364882B - Application of nitrogen/phosphorus co-doped carbon-coated cerium dioxide catalyst in degradation of antibiotic wastewater - Google Patents

Application of nitrogen/phosphorus co-doped carbon-coated cerium dioxide catalyst in degradation of antibiotic wastewater Download PDF

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CN115364882B
CN115364882B CN202110536451.7A CN202110536451A CN115364882B CN 115364882 B CN115364882 B CN 115364882B CN 202110536451 A CN202110536451 A CN 202110536451A CN 115364882 B CN115364882 B CN 115364882B
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CN115364882A (en
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李轶
李壮
展思辉
谢良波
崔玉昆
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Tianjin University
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Abstract

The invention discloses an application of a nitrogen/phosphorus co-doped carbon-coated cerium dioxide catalyst in degrading antibiotic wastewater, and a preparation method of the cerium dioxide catalyst comprises the following steps: ceO is added with 2 Mixing nano particles, phytic acid, aniline and water to obtain a solution B, dropwise adding an ammonium persulfate aqueous solution into the solution B, performing ultrasonic treatment to obtain a product, centrifuging the product, collecting a precipitate obtained by centrifugation, washing, drying, and calcining at 700-1100 ℃ for 2-5 h in a nitrogen or inert gas environment to obtain the cerium oxide catalyst. The ceria catalyst of the invention can degrade antibiotic wastewater, and the antibiotic can be ciprofloxacin, tetracycline hydrochloride, enrofloxacin and/or sulfamethoxazole, has universality, and in addition, the ceria catalyst of the invention still maintains higher degradation efficiency and better circulation in a wider pH rangeStability.

Description

Application of nitrogen/phosphorus co-doped carbon-coated cerium dioxide catalyst in degradation of antibiotic wastewater
Technical Field
The invention belongs to the technical field of treatment of refractory pollutants by an electro-Fenton-like method, and particularly relates to application of a nitrogen/phosphorus co-doped carbon-coated cerium oxide catalyst in degradation of antibiotic wastewater.
Background
With the wide application of antibiotics in the world, more and more potential safety problems are exposed, such as drug-resistant pathogens and superbacteria, so that people are concerned about the environment and the health of the antibiotics, and the antibiotics become one of the hot spots of the current international research. So far, the presence of various antibiotics has been detected in many countries and regions, and the components thereof are also various. Ciprofloxacin (CIP), a third generation quinolone antibiotic, has been detected in sewage treatment plants, causing antibiotic contamination. However, due to the good chemical stability and biodegradability of ciprofloxacin, efficient removal of ciprofloxacin remains a major challenge for conventional wastewater treatment processes.
In recent years, advanced Oxidation Processes (AOP) such as Fenton, electro-Fenton-like, photocatalytic, electro-optic Fenton and ozone oxidation have been widely used for mineralization of various refractory organic pollutants. Wherein, the electro-Fenton-like technology is an environment-friendly process technology, which activates oxygen on the surface of a cathode to generate hydrogen peroxide (H) 2 O 2 ) And the like, can realize effective treatment of pollutants. In general, degradation of contaminants in an electro-Fenton-like process involves three factors: (1) Cathode in situ generation of H 2 O 2 Is a rate of (2); (2) the type and amount of Reactive Oxygen Species (ROS); and (3) selecting and recycling the catalyst. Due to the limitations of classical homogeneous Fenton systems, such as pH limitation, iron sludge formation and H 2 O 2 Excessive use of reagents, etc., makes more and more people more inclined to choose heterogeneous and non-iron type catalysts. In addition, most of the catalysts are affected by the pH value of the wastewater at present, and the use range of the pH value of the catalyst is enlarged to solve the problem of pollutant reduction in the wastewaterThe solution is of great importance. Therefore, it is important to design a heterogeneous catalyst, oxygen is rapidly activated at the cathode, more and stronger ROS are generated, and effective degradation of pollutants is realized in a wider pH range.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a nitrogen/phosphorus co-doped carbon-coated cerium oxide catalyst (CeO) 2 -NPC) by hydrothermal synthesis of CeO 2 The nano particles, then aniline is taken as a nitrogen source, phytic acid is taken as a phosphorus source, and the CeO is realized at high temperature 2 The composite of the nano particles can obtain the cerium oxide catalyst (CeO) 2 -NPC)。
Another object of the present invention is to provide a cerium oxide catalyst (CeO) obtained by the above-mentioned preparation method 2 -NPC)。
Another object of the present invention is to provide a ceria catalyst (CeO) 2 -NPC) for degrading antibiotic wastewater, ceO 2 The NPC catalyst is uniformly dispersed in the simulated wastewater, carbon Felt (CF) is used as a cathode, pt sheets are used as anodes, and the effective degradation of antibiotics is realized under the conditions of an external power supply and oxygen.
The aim of the invention is achieved by the following technical scheme.
Nitrogen/phosphorus co-doped carbon-coated cerium dioxide catalyst (CeO) 2 -NPC), comprising the steps of:
1) Dissolving cerium salt in acetic acid aqueous solution, performing ultrasonic treatment, and dropwise adding ethylene glycol under stirring to obtain solution A, wherein the ratio of the mass parts of the cerium salt to the volume parts of the acetic acid aqueous solution is (1.5-2.5): (3.5-4.5), wherein the ratio of the acetic acid aqueous solution to the ethylene glycol is (3.5-4.5) in parts by volume: (60-70);
in the step 1), the ratio of acetic acid to water in the acetic acid aqueous solution is (0.5-1.5) in parts by volume: (0.5-1.5).
In the step 1), the cerium salt is Ce (NO) 3 ) 3 ·6H 2 O。
2) Dissolving the saidHeating the solution A at 180-200 ℃ for 1-5 h, naturally cooling to room temperature of 20-25 ℃, centrifuging, washing and drying to obtain CeO 2 A nanoparticle;
3) CeO obtained in the step 2) is prepared 2 Mixing nano particles, phytic acid, aniline and water to obtain a solution B, dropwise adding an ammonium persulfate aqueous solution into the solution B, and performing ultrasonic treatment to obtain a product, wherein the CeO is 2 The ratio of the mass parts of the nano particles, the mass parts of the phytic acid, the mass parts of the aniline and the mass parts of the ammonium persulfate in the ammonium persulfate aqueous solution is (0.05-0.25): (0.002-0.008): 0.025: (0.00125 to 0.005);
in the step 3), the concentration of ammonium persulfate in the ammonium persulfate aqueous solution is 1.25 to 5.0 mol.L -1 。
In the step 3), the concentration of the phytic acid in the solution B is 0.2 to 0.8 mol.L -1 。
4) Centrifuging the product, collecting precipitate obtained by centrifugation, washing, drying, calcining for 2-5 h at 700-1100 ℃ in nitrogen or inert gas environment to obtain the cerium oxide catalyst (CeO) 2 -NPC)。
In the technical scheme, the unit of the parts by weight is g, the unit of the parts by volume is mL, and the unit of the parts by weight of the substances is mol.
In the steps 2) and 4), the washing is alternately performed by distilled water and absolute ethyl alcohol, and each alternate method comprises the following steps: adding distilled water, centrifuging, removing supernatant, adding absolute ethanol, centrifuging, and removing supernatant.
In the steps 2) and 4), the drying temperature is 60-80 ℃ and the drying time is 3-10 h.
Cerium oxide catalyst (CeO) obtained by the above preparation method 2 -NPC)。
The above ceria catalyst (CeO) 2 -NPC) in degrading antibiotic wastewater.
In the above technical scheme, the antibiotics are Ciprofloxacin (CIP), tetracycline hydrochloride (TTC), enrofloxacin (ENR) and/or Sulfamethoxazole (SMX).
In the above technical solution, the pH of the antibiotic wastewater is 2 to 7, preferably ph=3.
In the above-described embodiments, the ceria catalyst (CeO 2 -NPC) degrading antibiotics in antibiotic wastewater: the ceria catalyst is put into the electrolyte-containing antibiotic wastewater, oxygen is introduced into the antibiotic wastewater for 30-180 min, a carbon felt is used as a cathode, a platinum sheet is used as an anode, and a voltage of 2-6V is applied.
In the technical proposal, the flow rate of the introduced oxygen is 90-110 mL.min -1 。
In the technical scheme, the amount of the cerium oxide catalyst added into each 60mL of antibiotic wastewater is 6-12 mg.
In the technical proposal, the concentration of electrolyte in the antibiotic wastewater is 0.03 to 0.07 mol.L -1 。
In the technical proposal, the concentration of the antibiotics in the antibiotic wastewater is 40 to 60 mg.L -1 。
Compared with the prior art, the invention has the following advantages and effects:
1. with CeO 2 Nanoparticles and CeO 2 Compared with NC catalyst, the ceria catalyst (CeO 2 NPC) has a larger specific surface area and more oxygen vacancies, facilitating the adsorption and degradation of antibiotics.
2. The ceria catalyst (CeO) of the invention 2 NPC) still maintains high degradation efficiency over a wide pH range (2-7).
3. The ceria catalyst (CeO) of the invention 2 NPC) has stability and universality.
Drawings
FIG. 1 is a graph of contact angles of a carbon mat before (a) and after (b) pretreatment;
FIG. 2 is an SEM, TEM, and energy dispersive X-ray spectroscopy (EDS) elemental map, where a is the CeO obtained in example 12 2 SEM image of nanoparticles, b is CeO obtained in example 13 2 SEM image of NC catalyst, c is the cerium oxide catalyst (CeO) obtained in example 2 2 -NPC) SEM image of the sample,d and e are the cerium oxide catalyst (CeO) obtained in example 2 2 -NPC), f-j is the cerium oxide catalyst (CeO) obtained in example 2 2 -NPC) energy dispersive X-ray spectroscopy (EDS) elemental mapping;
FIG. 3 shows CeO obtained in example 12 2 Nanoparticles, ceO obtained in example 13 2 NC catalyst and cerium oxide catalyst (CeO) obtained in example 2 2 -NPC);
FIG. 4 shows a cerium oxide catalyst (CeO) obtained in example 2 2 -NPC) porosity characteristics (pore size distribution of specific surface area);
FIG. 5 shows CeO obtained in example 13 2 NC catalyst and cerium oxide catalyst (CeO) obtained in example 2 2 -NPC);
FIG. 6 shows a cerium oxide catalyst (CeO) obtained in example 2 2 -XPS full spectrum (a) of NPC) and high resolution XPS spectra of C1s (b), ce 3d (C), O1s (d), N1s (e) and P2P (f);
FIG. 7 shows the CIP degradation efficiency change (with different CeO) of examples 14 to 18 2 Dosage).
FIG. 8 is a graph showing CIP degradation efficiency variation (different aniline/ammonium persulfate molar ratios) for examples 15, 19 and 20;
FIG. 9 is a graph of CIP degradation efficiency variation (different temperatures) for examples 15 and 21-24, where a is CIP degradation efficiency and b is apparent reaction rate constant comparison;
FIG. 10 shows CIP degradation efficiency changes (different pH) for examples 15 and 25-29;
FIG. 11 is CIP degradation efficiency variation for examples 15, 30 and 31;
FIG. 12 is CIP degradation efficiency variation for examples 15, 32 and 33;
FIG. 13 shows the change in the mineralization of CIP in examples 15 and 33, wherein a is the change in Total Organic Carbon (TOC) removal upon degradation of CIP in examples 15 and 33, and b is the change in Mineralization Current Efficiency (MCE) upon degradation of CIP in examples 15 and 33;
FIG. 14 shows a cerium oxide catalyst (CeO) obtained in example 2 2 -NPC) stability test;
FIG. 15 shows the ceria obtained in example 2Catalyst (CeO) 2 -NPC).
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The purity and manufacturer of the drug product according to the following examples are as follows:
the types and manufacturers of the instruments involved in the following examples are as follows:
the carbon felt is purchased from Shanghai Jie carbon materials Co., ltd (China) and requires further treatment for use. Firstly, cutting the purchased three-dimensional carbon felt into 5cm multiplied by 3cm multiplied by 0.6cm, soaking in 10wt%H 2 O 2 In the aqueous solution, it was heated in a constant temperature oven at 90℃for 3 hours, after which the carbon felt was further immersed in 10wt% aqueous HCl, then heated in a constant temperature oven at 90℃for 1 hour, cooled, rinsed with ultrapure water and finally dried overnight at 60 ℃.
Fig. 1 shows contact angles of carbon felt before (a) and after (b) pretreatment. The carbon felt after treatment was found to have a smaller contact angle of about 115 ° and a contact angle before pretreatment of about 125 °. Obviously, after the carbon felt is treated by hydrogen peroxide and hydrochloric acid, the hydrophilicity of the carbon fiber surface is enhanced, and the balance of the hydrophilicity and the hydrophobicity is balanced to H 2 O 2 Is of critical importance in the generation of (a). In the case of a cathode without a gas diffusion layer, the problems caused by the electrolyte reaching the surface of the cathode with dissolved oxygen can be solved.
In the following steps 2) and 4) of examples 1 to 11, washing was performed alternately with distilled water and absolute ethanol, each of the alternately performed methods being: adding distilled water, centrifuging, removing supernatant, adding absolute ethanol, centrifuging, and removing supernatant.
The absorbance value and the concentration of the antibiotic satisfy the lambert-beer law formula, namely A=epsilon×C×l, wherein A is absorbance, epsilon is a molar absorbance coefficient, C is the concentration of the antibiotic in the solution, and l is the thickness of the liquid in the cuvette. Therefore, the absorbance value is positively correlated with the concentration, the absorbance at lambda=276 nm is measured at a selected time point, and the absorbance value is substituted into a lambert-beer law formula to obtain the concentration value of the antibiotics. The degradation efficiency is calculated by the following formula: w= (C 0 –C t )/C 0 X 100%, where C 0 Concentration value of antibiotic before degradation, C t Is the concentration value of the antibiotic after degradation.
Examples 1 to 11
Nitrogen/phosphorus co-doped carbon-coated cerium dioxide catalyst (CeO) 2 -NPC), comprising the steps of:
1) Preparation of aqueous acetic acid solution and Ce (NO) as cerium salt 3 ) 3 ·6H 2 The ratio of acetic acid to water in the acetic acid aqueous solution is 1:1. dissolving cerium salt in acetic acid aqueous solution, carrying out ultrasonic treatment for 10min, and dropwise adding ethylene glycol under the condition of intense stirring to obtain solution A, wherein the ratio of the mass parts of cerium salt to the volume parts of the acetic acid aqueous solution is 2:4, the unit of the mass parts is g, the unit of the volume parts is mL, and the ratio of the acetic acid aqueous solution to the ethylene glycol is 4:60;
2) Heating the solution A at 180 ℃ for 2.5h in a hydrothermal reaction kettle, naturally cooling to room temperature of 20-25 ℃, centrifuging, washing and centrifuging the obtained solid, and drying at 65 ℃ for 5h to obtain CeO 2 A nanoparticle;
3) CeO obtained in the step 2) is prepared 2 Mixing the nano particles, phytic acid, aniline and water to obtain a solution B, wherein the concentration of phytic acid in the solution B is 0.5 mol.L -1 . And (3) dropwise adding the ammonium persulfate aqueous solution into the solution B, and performing ultrasonic treatment until the solution becomes dark green to obtain a product. Wherein, ceO 2 The mass portion of the nano particles, the mass portion of the phytic acid,The ratio of the parts by weight of the aniline to the parts by weight of the ammonium persulfate in the ammonium persulfate aqueous solution is X, the concentration of the ammonium persulfate in the ammonium persulfate aqueous solution is Y, the unit of parts by weight is g, and the unit of parts by weight of the substances is mol;
4) Centrifuging the product, collecting precipitate, washing, drying at 60deg.C for 8 hr, and standing in a high temperature tube furnace at 4deg.C for 4 min under nitrogen atmosphere -1 Is heated to T ℃ and calcined at T ℃ for 2 hours to obtain the cerium oxide catalyst (CeO) 2 -NPC)。
TABLE 1
Example 12
CeO (CeO) 2 A method of preparing nanoparticles comprising the steps of:
1) Preparation of aqueous acetic acid solution and Ce (NO) as cerium salt 3 ) 3 ·6H 2 The ratio of acetic acid to water in the acetic acid aqueous solution is 1:1. dissolving cerium salt in an acetic acid aqueous solution, carrying out ultrasonic treatment for 10min, and dropwise adding ethylene glycol under a vigorous stirring condition for 30min to obtain a solution A, wherein the ratio of the mass parts of the cerium salt to the volume parts of the acetic acid aqueous solution is 2:4, the unit of the mass parts is g, the unit of the volume parts is mL, and the ratio of the acetic acid aqueous solution to the ethylene glycol is 4:60;
2) Heating the solution A at 180 ℃ for 2.5h in a hydrothermal reaction kettle, naturally cooling to room temperature of 20-25 ℃, centrifuging, washing and centrifuging the obtained solid, and drying at 65 ℃ for 5h to obtain CeO 2 A nanoparticle;
example 13
CeO (CeO) 2 -NC catalyst preparation method comprising the steps of:
the preparation method of example 13 is substantially the same as that of example 2, and is notThe same is only that: by hydrochloric acid (1 mol.L) -1 ) The phytic acid in example 2 was replaced and the amount of hydrochloric acid was adjusted. The pH was adjusted to the pH of solution B in example 2 by adjusting the amount of hydrochloric acid used.
A, b and c in FIG. 2 are respectively CeO obtained in example 12 in this order 2 Nanoparticles, ceO obtained in example 13 2 NC catalyst and cerium oxide catalyst (CeO) obtained in example 2 2 -NPC), from which it can be seen that CeO 2 The nanoparticle showed regular spherical morphology, but after introduction of heteroatoms C, N or P, it was CeO obtained in example 13 2 NC catalyst and cerium oxide catalyst (CeO) obtained in example 2 2 NPC), the morphology becomes irregular obviously, which may be that the carbon skeleton is formed in CeO 2 As a result of the surface loading. In FIG. 2, d and e are shown the ceria catalyst (CeO) obtained in example 2 2 -NPC) and found to have significant lattice fringesThese fringes may be associated with CeO 2 (111) Face or CePO 4 (120) Surface-related; meanwhile, energy dispersive X-ray spectroscopy (EDS) element spectrum analysis is also carried out, and C, ce, O, N and P elements are detected to exist, which shows that the cerium oxide catalyst (CeO) is successfully synthesized 2 NPC) (f-j of fig. 2, the detection elements are C, ce, O, N and P in order).
FIG. 3 shows CeO obtained in example 12 2 Nanoparticle (CeO) 2 ) CeO obtained in example 13 2 NC catalyst (CeO) 2 -NC) and the cerium oxide catalyst (CeO) obtained in example 2 2 -NPC). From the figure, ceO 2 Nanoparticles and CeO 2 Characteristic peaks of the NC catalyst appear at 28.6 °, 33.1 °, 47.5 °, and 56.4 °, corresponding to CeO, respectively 2 (111), (200), (220) and (311) crystal planes (PDF # 43-1002); whereas CeO 2 The XRD pattern of the NPC catalyst shows CePO 4 The characteristic peaks of (3) at 18.9 °, 21.2 °, 25.4 °, 26.9 °, 28.8 ° and 31.1 ° correspond to (011), (-111), (020), (200) (120) and (012) crystal planes (pdf#32-0199), respectively. CePO (CePO) 4 The presence of (C) indicates Ce 4+ Reduction to Ce at high temperature 3+ And with PO 4 3- Reacting to generate CePO 4 。
The ceria catalyst (CeO) obtained in example 2 was further studied by nitrogen adsorption-desorption isotherms 2 -NPC) (fig. 4). From the figure, it was found that the ceria catalyst (CeO) 2 NPC) exhibits a typical IV isotherm with mesoporous structure and H4 hysteresis loop, ceria catalyst (CeO) 2 -NPC) of 194.97m 2 ·g -1 The pore diameter is 16.84nm, has larger specific surface area and pore diameter, and shows better adsorption and catalysis performance.
Raman spectroscopy was used to study material defects and to further identify the catalytically active sites in the electro-Fenton-like process. As a result, as shown in FIG. 5, there were two distinct peaks in the spectrum, namely the D band (about 1325cm -1 ) And G band (about 1592 cm) -1 ) This indicates the presence of disordered carbon and graphitic carbon. In addition, the intensity ratio of D band and G band (I D /I G ) Is an important index reflecting the degree of carbon defects and structural disorder. With CeO obtained in example 13 2 The introduction of P causes I of the catalyst compared to NC catalyst D /I G A slight increase (1.18 vs.1.11) indicated a similar degree of carbon disorientation. Heteroatom doping is considered to be an effective way to improve the catalytic properties of materials. It is therefore necessary to understand the content and type of nitrogen or phosphorus dopants that affect the performance of the catalyst and to characterize it further.
The cerium oxide catalyst (CeO) obtained in example 2 2 -NPC) and high resolution XPS spectra of C1s, ce 3d, O1s, N1s and P2P are shown in fig. 6 a-f. The presence of C, ce, N, O and P spectrum signals confirm the presence of the ceria catalyst (CeO 2 -NPC). The high resolution C1s spectrum was deconvoluted into four peaks of 284.6eV, 285.0eV, 286.4eV, and 289.4eV, corresponding to c= C, C-O/c=n/C-P, C =o/C-N and O-c=o, respectively. The high resolution Ce 3d spectrum has complex but distinct features, and the peaks labeled u and v represent 3d, respectively 3/2 And 3d 5/2 Spin orbits, which are deconvoluted intoThe 8 peaks correspond to u '"(916.6 eV), u" (906.5 eV), u' (904.6 eV), u (902.9 eV), v '"(900.9 eV), v" (887.9 eV), v' (885.8 eV) and v (882.6 eV), respectively. The v 'and u' peaks are attributed to Ce 3+ 3d of species 10 4f 1 The other six peaks are attributed to Ce 4+ Species-corresponding 3d 10 4f 0 Status of the device. The high resolution O1s spectrum is deconvoluted into three peaks, wherein the peaks at 532.7-533.5eV, 531.0-531.7eV and 529.5-530.1eV are attributed to chemisorbed oxygen (O), respectively α ) Oxygen vacancy (O) β ) And lattice oxygen (O) γ ). The N1s spectrum was divided into three types of nitrogen, corresponding to pyridine N (398.6 eV), pyrrole N (399.7 eV) and graphite N (400.8 eV), respectively. The high resolution P2P signal can be split into two peaks at 133.6eV (P-N) and 132.8eV (P-C), indicating that both P and N are effectively doped into the carbon backbone. These results indicate that high levels of oxygen vacancies and graphite nitrogen facilitate oxygen adsorption and electron transfer, facilitating the electro-Fenton-like process.
Degradation test of antibiotic wastewater
The electro-Fenton-like activity of the catalyst was evaluated with the degradation efficiency of Ciprofloxacin (CIP). Specifically, 60mL of the solution contains Na 2 SO 4 (0.05mol·L -1 As electrolyte) and CIP (50mg.L -1 ) Is stored as degradation liquid in a cylindrical glass container by adding 0.5 mol.L -1 Sulfuric acid or sodium hydroxide adjusts the initial pH of the solution. The pretreated carbon felt is selected as a cathode, a platinum sheet is selected as an anode, and the distance between the two electrodes is 1.0cm. Then, 10mg of catalyst was added to the degradation liquid, and oxygen was continuously supplied (100 mL. Min -1 ) The method comprises the steps of carrying out a first treatment on the surface of the After 30min, application of 4V voltage began to degrade CIP. During the electro-Fenton-like process, 3mL of the degradation solution is absorbed over a selected time interval and the absorbance is measured by an ultraviolet-visible spectrophotometer. The catalyst used was the ceria catalyst (CeO) prepared in examples 1 to 13 2 -NPC)、CeO 2 Nanoparticles and CeO 2 One of the NC catalysts, initial pH and catalyst are detailed in Table 2.
TABLE 2
The CIP degradation effects of examples 14 to 18 are shown in FIG. 7, and the results of the study on the synthesis of cerium oxide catalyst (CeO 2 -NPC) CeO in process 2 Effect of dose on CIP degradation effect, it was found that with CeO, the catalysts obtained in examples 1 to 5 were electro-Fenton-like catalysts 2 The increase of the dosage shows the rising trend of the degradation efficiency of CIP, when CeO in X 2 After the value of the nanoparticle exceeds 0.1, the degradation efficiency of CIP tends to be stable with little change.
The CIP degradation effect of examples 15, 19 and 20 is shown in FIG. 8, the molar ratio of aniline/ammonium persulfate has significance for the synthesis of polyaniline, when the molar ratio of aniline/ammonium persulfate is 1:1, the degradation effect is relatively good.
The CIP degradation effect of examples 15 and 21 to 24 is shown as a in fig. 9, and the CIP degradation efficiency is remarkably improved with an increase in temperature and tends to be stable at around 1000 ℃. With a cerium oxide catalyst (CeO) prepared at 700 DEG C 2 NPC) (only 78.1%) compared to ceria catalyst (CeO) prepared at 1000 °c 2 NPC) is heterogeneous Fenton-like reagent, and the CIP degradation efficiency reaches 97.8% at 180min, which indicates that the roasting temperature has a significant effect on the catalyst performance. B in fig. 9 shows the apparent reaction rate constants of the CIP degradation effects at different temperatures, and the effect of temperature on CIP degradation effects can be more intuitively seen.
The CIP degradation effects of examples 15 and 25-29 are shown in FIG. 10, where CIP degradation efficiency reached a maximum at an initial pH of 3 and 97.8% at 180 min. With the initial pH value [ ]<3) Is reduced, H 2 O 2 Capturing protons in solution to generate H 3 O 2 + Leading to H 2 O 2 Reduced utilization rate, H + Has obvious inhibition effect on OH under the condition of strong acid. At the same time, with initial pHIncrease of%>3.0 The degradation efficiency of CIP is slightly reduced. At an initial pH of 7, the degradation efficiency of CIP drops to 83.7% at 180min, and it is likely that the catalyst becomes deactivated under neutral or even alkaline conditions to form Ce (OH) 4 Precipitation of Ce is inhibited 4+ /Ce 3+ The active site of the catalyst is reduced. In general, ceO 2 The NPC catalyst has no significant change in activity over a wide pH range, yet retains good CIP degradation performance.
The CIP degradation effects of examples 15, 30 and 31 are shown in FIG. 11, when CeO is used 2 In a system with nanoparticles as the electro-Fenton-like reagent, the degradation efficiency of CIP is only 6.9% and 62.5% at 60min and 180min respectively. At CeO 2 Surface incorporation of Nitrogen doped carbon (i.e. CeO) 2 -NC catalyst), the degradation efficiency of CIP increases to 21.9% and 78.4% at 60min and 180min, respectively. In particular by addition of P (i.e. ceria catalyst (CeO) 2 -NPC)) and at 60min and 180min, the CIP degradation efficiency reached 73.6% and 97.8%, respectively. By comparing the degradation effect of different types of catalysts on CIP, it was found that the catalyst was synthesized with a ceria catalyst (CeO 2 NPC) is an electro-Fenton-like reagent, which can significantly improve the degradation efficiency of CIP.
Example 32 (physical adsorption)
60mL of the mixture contains Na 2 SO 4 (0.05mol·L -1 ) And CIP (50 mg.L) -1 ) Is stored as degradation liquid in a cylindrical glass container by adding 0.5 mol.L -1 Sulfuric acid or sodium hydroxide adjusts the pH of the solution to 3. The pretreated carbon felt was immersed in the simulated wastewater and 10mg of ceria catalyst (CeO) was added thereto 2 NPC), stirring and continuously supplying oxygen for 180min (100 mL. Min) -1 ). During the physical adsorption process, 3mL of the degradation solution was absorbed over a selected time interval and the absorbance was measured by an ultraviolet-visible spectrophotometer.
Example 33 (electro-adsorption)
60mL of the mixture contains Na 2 SO 4 (0.05mol·L -1 ) And CIP (50 mg.L) -1 ) Is stored as degradation liquid in a cylindrical glass container by adding 0.5mol DEG CL -1 Sulfuric acid or sodium hydroxide adjusts the pH of the solution to 3. The pretreated carbon felt is selected as a cathode, a platinum sheet is selected as an anode, and the distance between the two electrodes is 1.0cm. Stirring and continuously supplying oxygen (100 mL. Min) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the After 30min, application of 4V voltage began to degrade CIP. During the electro-adsorption process, 3mL of the degradation solution was absorbed over a selected time interval and the absorbance was measured by an ultraviolet-visible spectrophotometer.
The effect of different degradation processes on CIP degradation was investigated by examples 15, 32-33 (fig. 12). Example 15 is an electro-Fenton-like process in which a voltage of 4V is applied and a cerium oxide catalyst (CeO) is added 2 -NPC); example 32 is physical adsorption in which a cerium oxide catalyst (CeO) 2 -NPC), but not energized; example 33 is an electro-adsorption process that is energized with an applied voltage of 4V, but without the addition of catalyst. As a result, it was found that the CIP removal rate was almost negligible in example 32, and was only 4.2% in 180min, and the CIP removal efficiency was improved to a certain extent in example 33, and was improved to 61.4% in 180 min. However, in the embodiment 15, the degradation efficiency of CIP is greatly improved, and 97.8% is achieved within 180min, which proves the superiority of the quasi-electro Fenton method.
The Total Organic Carbon (TOC) removal and Mineralization Current Efficiency (MCE) changes of CIP under both procedures of examples 15 and 33 were studied, as shown in fig. 13. The TOC analyzer (TOC-VCPH) is used to determine the Total Organic Carbon (TOC) value at a specific time point, and the TOC removal rate w' (TOC) in CIP degradation process is calculated by the formula (1) 0 TOC for a total organic carbon value of 0 time t Is the total organic carbon value at time t). The TOC removal effect of CIP was found to be significant in example 15 compared to the procedure of example 33, reaching 57.6% in 180min, consistent with the degradation effect of CIP. Based on the TOC data, the change in MCE is then explored from equation (2). In formula (2), n is 70, which allows for complete mineralization to CO 2 、H 2 The number of electrons consumed during CIP degradation at O and inorganic ions (formula (3)); f is Faraday constant (96485 C.mol) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the V is the total volume (L) of the degradation liquid; delta (TOC) is the reduction in TOC value (m.L) during CIP degradation -1 )；4.32×10 7 Is the conversion coefficient (=3600 s.h) -1 ×12000mg C·mol -1 ) The method comprises the steps of carrying out a first treatment on the surface of the m is the number of carbon atoms in CIP; i is an impressed current (A); t is the electrolysis time (h). Fig. 13 b shows the variation of MCE (%) under examples 15 and 33. It can be seen that the MCE was greatly improved compared to the example 33 process due to the rapid removal of TOC in the example 15 process, with MCE values of 16.4%, 8.4% and 6.2% at 1h, 2h and 3h electrolysis, respectively. Thus, cerium oxide catalyst (CeO) 2 NPC) has a higher mineralization efficiency and a lower energy consumption.
w'＝(TOC 0 -TOC t )/TOC 0 (1)
MCE(％)＝[nFVΔ(TOC)]/(4.32×10 7 ·mIt)×100％ (2)
C 17 H 18 FN 3 O 3 +31H 2 O→17CO 2 +3NH 4 + +68H + +F - +70e - (3)
The service life of the catalyst is a key factor influencing heterogeneous Fenton reaction, so a stability experiment of CIP degradation is performed to explore a cerium oxide catalyst (CeO) 2 -NPC) stability and reusability. With cerium oxide catalyst (CeO) 2 NPC) is an electro-Fenton-like catalyst, and three cycles of CIP electro-Fenton-like system degradation are performed according to example 15, wherein carbon felt and cerium oxide catalyst (CeO) are recovered each time 2 NPC), washed with distilled water, centrifuged and then dried at 60 ℃ for the next cycle. As shown in FIG. 14, after three continuous runs, the degradation efficiency was still 95.0% or more at 180min, verifying the ceria catalyst (CeO) 2 -NPC).
The electro-Fenton-like activity of the catalyst was evaluated by degradation effects of Ciprofloxacin (CIP), tetracycline hydrochloride (TTC), enrofloxacin (ENR) and Sulfamethoxazole (SMX), and the ceria catalyst (CeO) obtained in example 2 was examined 2 -NPC). Specifically, 60mL of the solution contains Na 2 SO 4 (0.05mol·L -1 ) And CIP/TTC/ENR/SMX (50mg.L) -1 ) Is stored as degradation liquid in a cylindrical glass container,by adding 0.5 mol.L -1 Sulfuric acid or sodium hydroxide adjusts the initial pH of the solution to 3. The pretreated carbon felt is selected as a cathode, a platinum sheet is selected as an anode, and the distance between the two electrodes is 1.0cm. Then, 10mg of ceria catalyst (CeO) was added to the degradation liquid 2 NPC), stirring and continuous supply of oxygen (100 mL. Min -1 ) The method comprises the steps of carrying out a first treatment on the surface of the After 30min, application of 4V voltage began to degrade CIP. During the electro-Fenton-like process, 3mL of the degradation solution is absorbed over a selected time interval and the absorbance is measured by an ultraviolet-visible spectrophotometer. As shown in fig. 15, in the electro-Fenton-like system, a ceria catalyst (CeO 2 NPC) showed strong degradation ability to all four pollutants, verifying the cerium oxide catalyst (CeO) 2 -NPC).
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.

Claims (11)

1. Use of a nitrogen/phosphorus co-doped carbon-coated ceria catalyst for degrading antibiotic wastewater, comprising: the ceria catalyst is put into the electrolyte-containing antibiotic wastewater, oxygen is introduced into the antibiotic wastewater for 30-180 min, a carbon felt is used as a cathode, a platinum sheet is used as an anode, and a voltage of 2-6V is applied, wherein the preparation method of the ceria catalyst comprises the following steps:
1) Dissolving cerium salt in acetic acid aqueous solution, performing ultrasonic treatment, and dropwise adding ethylene glycol under stirring to obtain solution A, wherein the ratio of the mass parts of the cerium salt to the volume parts of the acetic acid aqueous solution is (1.5-2.5): (3.5-4.5), wherein the ratio of the acetic acid aqueous solution to the ethylene glycol is (3.5-4.5) in parts by volume: (60-70);
2) Heating the solution A at 180-200 ℃ for 1-5 h, naturally cooling to room temperature of 20-25 ℃, centrifuging, washing and drying to obtain CeO 2 A nanoparticle;
3) CeO obtained in the step 2) is prepared 2 Mixing nano particles, phytic acid, aniline and water to obtain a solution B, dropwise adding an ammonium persulfate aqueous solution into the solution B, and performing ultrasonic treatment to obtain a product, wherein the CeO is 2 The ratio of the mass parts of the nano particles, the mass parts of the phytic acid, the mass parts of the aniline and the mass parts of the ammonium persulfate in the ammonium persulfate aqueous solution is (0.05-0.25): (0.002-0.008): 0.025: (0.00125 to 0.005);
4) Centrifuging the product, collecting a precipitate obtained by centrifugation, washing, drying, and calcining at 800-1100 ℃ for 2-5 h in the presence of nitrogen or inert gas to obtain the cerium oxide catalyst, wherein the unit of mass fraction is g, the unit of volume fraction is mL, and the unit of mass fraction of the substance is mol.
2. The use according to claim 1, characterized in that in said step 1), the ratio of acetic acid to water in the aqueous acetic acid solution is (0.5-1.5) in parts by volume: (0.5-1.5).
3. The use according to claim 1, wherein in step 1) the cerium salt is Ce (NO 3 ) 3 ·6H 2 O。
4. The use according to claim 1, wherein in said step 3), the concentration of ammonium persulfate in said aqueous solution of ammonium persulfate is 1.25 to 5.0 mol.l -1 。
5. The use according to claim 1, characterized in that in said step 3) the concentration of phytic acid in said solution B is between 0.2 and 0.8 mol-L -1 。
6. Use according to claim 1, wherein the antibiotic is ciprofloxacin, tetracycline hydrochloride, enrofloxacin and/or sulfamethoxazole.
7. The use according to claim 1, characterized in that the pH of the antibiotic wastewater is 2-7.
8. The use according to claim 1, wherein the flow rate of the introduced oxygen is 90-110 mL/min -1 。
9. The use according to claim 1, wherein the amount of the ceria catalyst added per 60mL of antibiotic wastewater is 6 to 12mg.
10. The use according to claim 1, wherein the concentration of electrolyte in the antibiotic wastewater is 0.03-0.07 mol.l -1 。
11. The use according to claim 1, characterized in that the concentration of antibiotics in the antibiotic wastewater is 40-60 mg-L -1 。
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