CN117623483A - Application of nickel-doped lanthanum-iron perovskite in degradation of antibiotics - Google Patents
Application of nickel-doped lanthanum-iron perovskite in degradation of antibiotics Download PDFInfo
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- CN117623483A CN117623483A CN202410107841.6A CN202410107841A CN117623483A CN 117623483 A CN117623483 A CN 117623483A CN 202410107841 A CN202410107841 A CN 202410107841A CN 117623483 A CN117623483 A CN 117623483A
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 31
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 30
- NNLJGFCRHBKPPJ-UHFFFAOYSA-N iron lanthanum Chemical compound [Fe].[La] NNLJGFCRHBKPPJ-UHFFFAOYSA-N 0.000 title claims description 15
- 230000015556 catabolic process Effects 0.000 title description 38
- 238000006731 degradation reaction Methods 0.000 title description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 229960001180 norfloxacin Drugs 0.000 claims abstract description 46
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims abstract description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 230000000593 degrading effect Effects 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000011240 wet gel Substances 0.000 claims abstract description 16
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 claims abstract description 7
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims abstract description 7
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 7
- 229960000740 enrofloxacin Drugs 0.000 claims abstract description 7
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 230000003115 biocidal effect Effects 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 4
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- 230000003213 activating effect Effects 0.000 claims description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
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- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an application of nickel-doped lanthanum-iron-perovskite in degrading antibiotics, wherein a nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst to activate H 2 O 2 Degrading antibiotics, wherein the antibiotics comprise one or more of norfloxacin, ciprofloxacin, enrofloxacin or tetracycline hydrochloride, and the preparation method of the nickel-doped lanthanum-iron-perovskite composite material comprises the following steps: laCl is added 3 ·7H 2 O、FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 O and citric acid are dissolved in deionized water to form a mixed solution; evaporating the water content of the mixed solution to obtain wet gel, and drying the wet gel to obtain xerogel; pulverizing the xerogel and heating at least 400 DEG CAnd (3) calcining at high temperature, and cooling to room temperature to obtain the nickel-doped lanthanum-iron-perovskite composite material. The nickel-doped lanthanum-iron-perovskite composite material prepared by the invention is used as a catalyst to activate H under the irradiation of sunlight or xenon lamp 2 O 2 Degrading antibiotics such as norfloxacin, ciprofloxacin, enrofloxacin or tetracycline hydrochloride.
Description
Technical Field
The invention relates to the technical field of antibiotic degradation, in particular to application of nickel-doped lanthanum-iron perovskite in degradation of antibiotics.
Background
With the rapid development of medicine, antibiotic medicines are widely applied to human beings and animals, and make great contribution to preventing bacterial infection, but antibiotics cannot be completely absorbed by human metabolic systems, more than 75% of antibiotics can be digested in the form of feces and enter into water systems, and if the pollutant treatment technology is improper, the ecological system and human health are both potentially threatened.
Norfloxacin (NOR) is a representative class of broad-spectrum antibiotics that are often detected in surface, ground and tap water. NOR is difficult to degrade in municipal sewage treatment facilities by conventional biological methods due to its limitation of antibacterial properties. Furthermore, the presence of NOR can even cause potential ecological and genetic toxicity to aquatic animals and plants. The traditional methods for removing antibiotics in wastewater have the defects of electrochemical advanced oxidation, bioelectrochemical technology, biological method, membrane filtration method and the like, but the traditional treatment methods have the defects of high cost, low removing capacity and the like, so that the further practical application of the traditional treatment methods is limited.
The photocatalysis technology has the advantages of high efficiency, low cost, wide adsorbent, good recoverability, less secondary pollution and the like, and is considered as the most promising method for eliminating low-concentration antibiotics. In recent years, perovskite-based oxides have been widely used as a multifunctional material in the fields of photoelectrochemistry and catalysis. Wherein LaFeO 3 Is a typical perovskite catalyst, has the characteristics of light corrosion resistance, low cost, no harm and the like, but limits LaFeO due to the high recombination of electron-hole pairs and the low redox capacity of narrow band gap 3 Besides, the perovskite material is adopted as a catalyst, so that the perovskite material has better response to ultraviolet light, and only a small amount of light is absorbed in the visible light range, namely, in the actual wastewater treatment process, an ultraviolet light source device is required to be additionally arrangedThe auxiliary irradiation treatment of the antibiotic wastewater causes complicated treatment process and high energy consumption, and on one hand, the method does not meet the national energy-saving requirement, and on the other hand, the treatment cost of the antibiotic wastewater is increased, so that the method is still further improved.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the application of the nickel-doped lanthanum-iron perovskite in degrading antibiotics.
The invention is realized by the following technical scheme:
the preparation method of the nickel-doped lanthanum-iron perovskite comprises the following steps:
s1, laCl 3 ·7H 2 O、FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 O and citric acid are dissolved in deionized water to form a mixed solution;
s2, evaporating the water of the mixed solution to obtain wet gel, and drying the wet gel to obtain xerogel;
s3, crushing the xerogel, calcining at a high temperature of at least 400 ℃, and cooling to room temperature to obtain the nickel-doped lanthanum-iron-perovskite composite material.
According to the above technical solution, preferably, in step S1, the LaCl 3 ·7H 2 O、FeCl 3 ·7H 2 The molar ratio of the mixture of O and the citric acid is 1:2.5.
according to the above technical solution, preferably, in step S1, the FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is 3:7-7:3.
According to the above technical scheme, preferably, in step S1, 0.02mol of LaCl is added 3 ·7H 2 O、0.01mol FeCl 3 ·7H 2 O、0.01mol Ni(NO 3 ) 2 ·6H 2 O and 0.1mol of citric acid are dissolved in 300mL of deionized water to form a mixed solution, and the mixed solution is stirred for 20-40min.
The patent also discloses application of the nickel-doped lanthanum-iron perovskite in degrading antibiotics, and a preparation method based on the nickel-doped lanthanum-iron perovskiteThe nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst to activate H 2 O 2 Degrading the antibiotics.
According to the above technical scheme, preferably, the antibiotic is norfloxacin.
According to the technical scheme, preferably, 1.0g/L nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst in an acidic environment, and 15mM of H is activated under irradiation of visible light 2 O 2 Degrading norfloxacin.
According to the above technical scheme, preferably, the nickel doped lanthanum-iron-perovskite composite material is used as a catalyst to activate H under irradiation of sunlight or a xenon lamp 2 O 2 Degrading the antibiotics.
According to the above technical scheme, preferably, the antibiotic is ciprofloxacin, enrofloxacin or tetracycline hydrochloride.
The beneficial effects of the invention are as follows:
the invention adopts a sol-gel method to prepare the Ni-doped LaFeO 3 Composite material, which is used as catalyst to activate H 2 O 2 The antibiotic is degraded, the band gap energy of the catalyst can be reduced by doping Ni element, and meanwhile, the perovskite composite material can generate more photocurrent under the excitation of light by doping Ni element, so that the separation capability of carriers is enhanced, and the catalytic activity of the perovskite composite material is improved; meanwhile, the nickel-doped lanthanum-iron-perovskite composite material prepared by the method is used as a catalyst, so that antibiotics can be effectively degraded under different illumination conditions, and in the actual antibiotic wastewater treatment process, the equivalent catalytic efficiency can be obtained under natural light without additional ultraviolet light source equipment, so that the treatment cost of the antibiotic wastewater is reduced, and the potential application of the photocatalyst in the natural environment is enhanced; in addition, the nickel-doped lanthanum-iron-perovskite composite material prepared by the method is used as a catalyst, has universal applicability to removal of various antibiotic pollutants in a visible light reaction system, and has higher application and popularization values.
Drawings
FIG. 1 shows LaFeO of the present invention 3 SEM images of (a).
FIG. 2 is the LF of the present invention 0.3 N 0.7 SEM image of O.
FIG. 3 is the LF of the present invention 0.7 N 0.3 SEM image of O.
FIG. 4 is the LF of the present invention 0.5 N 0.5 SEM image of O.
FIG. 5 is LaFeO 3 And Ni doped LaFeO 3 XPS full spectrum of catalyst in the binding energy range of 0-1200 eV.
FIG. 6 is LFO, LF 0.3 N 0.7 O、LF 0.5 N 0.5 O and LF 0.7 N 0.3 UV-visible diffuse reflectance absorption spectrum of O.
FIG. 7 is LFO, LF 0.3 N 0.7 O、LF 0.5 N 0.5 O and LF 0.7 N 0.3 O (ahv) 2 Tauc plot of vs (hv).
Fig. 8 is LFO and LF 0.5 N 0.5 EIS diagram of O.
Fig. 9 is LFO and LF 0.5 N 0.5 Transient photocurrent response plot of O.
FIG. 10 is LFO, LF 0.3 N 0.7 O、LF 0.5 N 0.5 O and LF 0.7 N 0.3 Influence of O on NOR degradation.
Fig. 11 is LFO and LF 0.5 N 0.5 Effect of different initial pH values of O on NOR degradation.
Fig. 12 is LFO and LF 0.5 N 0.5 O is different from H 2 O 2 Effect of concentration on NOR degradation.
Fig. 13 is LFO and LF 0.5 N 0.5 Influence of different addition amounts of O on NOR degradation.
FIG. 14 is the effect on NOR degradation for different reaction systems.
Fig. 15 is LFO and LF 0.5 N 0.5 Effect of different light sources on NOR degradation.
Fig. 16 is LF 0.5 N 0.5 The degradation effect of O on other antibiotics is schematically shown.
Fig. 17 is LF 0.5 N 0.5 Influence on NOR degradation under O recycling.
FIG. 18 is a view of the product after initial and repeated useLF 0.5 N 0.5 XRD pattern of O.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, so that those skilled in the art can better understand the technical solutions of the present invention. All other embodiments, based on the embodiments of the invention, which would be apparent to one of ordinary skill in the art without making any inventive effort are intended to be within the scope of the invention.
Example 1: the invention comprises the following steps:
s1, laCl 3 ·7H 2 O、FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 O and citric acid are dissolved in deionized water to form a mixed solution, wherein LaCl 3 ·7H 2 O、FeCl 3 ·7H 2 The molar ratio of the mixture of O and the citric acid is 1:2.5 FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is 3:7-7:3;
s2, evaporating the water of the mixed solution to obtain wet gel, and drying the wet gel to obtain xerogel;
s3, crushing the xerogel, calcining at a high temperature of at least 400 ℃, and cooling to room temperature to obtain the nickel-doped lanthanum-iron-perovskite composite material.
Example 2: the invention comprises the following steps:
s1, 0.02mol of LaCl 3 ·7H 2 O、0.01mol FeCl 3 ·7H 2 O、0.01mol Ni(NO 3 ) 2 ·6H 2 O and 0.1mol of citric acid are dissolved in 300mL of deionized water to form a mixed solution, and the mixed solution is stirred for 20 to 40 minutes; in this case, stirring is preferably carried out for 30min under a 500r/min magnetic stirrer.
S2, transferring the mixed solution into a constant-temperature water bath kettle at 80 ℃ to evaporate water to obtain wet gel, and then drying the wet gel in an oven at 120 ℃ for 24 hours to obtain xerogel.
S3, crushing, grinding and moving the xerogel to a crucible, putting the crucible into a tube furnace, and setting the heating rate of the tube furnace to 5 ℃ and min -1 Calcining in air at 400deg.C for 2 hr to remove organic substances, andheating to 800 ℃ and calcining in air for 2 hours, and cooling to room temperature to obtain the nickel doped lanthanum-iron perovskite composite material, namely LaFe 0.5 Ni 0.5 O 3 Composite material, in this example denoted LF 0.5 N 0.5 O。
Example 3: the invention comprises the following steps:
s1, 0.02mol of LaCl 3 ·7H 2 O、0.006mol FeCl 3 ·7H 2 O、0.014mol Ni(NO 3 ) 2 ·6H 2 O and 0.1mol of citric acid are dissolved in 300mL of deionized water to form a mixed solution, and the mixed solution is stirred for 20 to 40 minutes; in this case, stirring is preferably carried out for 30min under a 500r/min magnetic stirrer.
S2, transferring the mixed solution into a constant-temperature water bath kettle at 80 ℃ to evaporate water to obtain wet gel, and then drying the wet gel in an oven at 120 ℃ for 24 hours to obtain xerogel.
S3, crushing, grinding and moving the xerogel to a crucible, putting the crucible into a tube furnace, and setting the heating rate of the tube furnace to 5 ℃ and min -1 Calcining for 2 hours in air at 400 ℃ to remove organic matters, then heating to 800 ℃ to calcine for 2 hours, and cooling to room temperature to obtain the nickel doped lanthanum-iron-perovskite composite material, namely LaFe 0.3 Ni 0.7 O 3 Composite material, in this example denoted LF 0.3 N 0.7 O。
Example 4: the invention comprises the following steps:
s1, 0.02mol of LaCl 3 ·7H 2 O、0.014mol FeCl 3 ·7H 2 O、0.006mol Ni(NO 3 ) 2 ·6H 2 O and 0.1mol of citric acid are dissolved in 300mL of deionized water to form a mixed solution, and the mixed solution is stirred for 20 to 40 minutes; in this case, stirring is preferably carried out for 30min under a 500r/min magnetic stirrer.
S2, transferring the mixed solution into a constant-temperature water bath kettle at 80 ℃ to evaporate water to obtain wet gel, and then drying the wet gel in an oven at 120 ℃ for 24 hours to obtain xerogel.
S3, crushing, grinding and moving the xerogel to a crucible, putting the crucible into a tube furnace, and setting the heating rate of the tube furnace to 5 ℃ and min -1 Calcining in air at 400deg.C for 2 hr to remove organic matters, heating to 800deg.C, calcining in air for 2 hr, and cooling to room temperatureThen the nickel doped lanthanum-iron perovskite composite material is obtained, namely LaFe 0.7 Ni 0.3 O 3 Composite material, in this example denoted LF 0.7 N 0.3 O。
Control group: the invention comprises the following steps:
s1, 0.02mol of LaCl 3 ·7H 2 O、0.02mol FeCl 3 ·7H 2 O and 0.1mol of citric acid are dissolved in 300mL of deionized water to form a mixed solution, and the mixed solution is stirred for 20 to 40 minutes; in this case, stirring is preferably carried out for 30min under a 500r/min magnetic stirrer.
S2, transferring the mixed solution into a constant-temperature water bath kettle at 80 ℃ to evaporate water to obtain wet gel, and then drying the wet gel in an oven at 120 ℃ for 24 hours to obtain xerogel.
S3, crushing, grinding and moving the xerogel to a crucible, putting the crucible into a tube furnace, and setting the heating rate of the tube furnace to 5 ℃ and min -1 Calcining for 2 hours in air at 400 ℃ to remove organic matters, then heating to 800 ℃ to calcine for 2 hours, and cooling to room temperature to obtain the nickel doped lanthanum-iron-perovskite composite material, namely LaFeO 3 The composite material, in this case denoted LFO.
FIGS. 1-4 show the observation of the original LaFeO by SEM 3 And Ni-doped LaFeO3 catalyst surface morphology features. As shown in FIG. 1, the LFO nano-particles have a network morphology consisting of 20-30nm ellipsoids, and LF 0.5 N 0.5 O is formed by irregular nano particle agglomeration, the surface is smooth and clear, and the particle size is about 10-20nm. The irregular aggregate structure leaves a rich pore structure on its surface, making it easy for contaminants to attach to the LF 0.5 N 0.5 O catalyst surface. The smaller the catalyst size, the better the light radiation and H 2 O 2 Promotes the transfer of photogenerated electrons and the formation of free radicals, thereby improving catalytic efficiency.
As shown in fig. 5, LFO and LF analysis using X-ray photoelectron spectroscopy (XPS) 0.5 N 0.5 Chemical composition and elemental valence of O, laFeO 3 And Ni doped LaFeO 3 XPS full spectrum of catalyst in 0-1200eV binding energy range, ni 2p spectral characteristic shows that Ni is doped into LaFeO 3 Among perovskite crystals.
The optical absorption properties of the catalyst are shown by ultraviolet-visible (UV-Vis) Diffuse Reflectance Spectroscopy (DRS) experiments. FIG. 6 shows LaFeO 3 The absorption band edge of (C) appears at about 600nm, and the absorbance is highest near 230nm, indicating LaFeO 3 Has better response to ultraviolet light and only small light absorption in the visible light range. While Ni-doped LaFeO 3 The absorption band edge of (2) is shifted toward the near infrared region, and the absorbance gradually increases in the visible region of 400 to 800 nm. Furthermore, laFeO is estimated from the Kubelka-Munk function and the Tauc-plot equation 3 And Ni doped LaFeO 3 Band gap value of the modified material. Utilization (alpha h v) 2 And drawing the hν, and extrapolating to the intersection point of the abscissa by utilizing the straight line part to obtain the band gap width value. The results in FIG. 7 show that the band gap of LFO is 2.20eV, and after doping with Ni, LF 0.3 N 0.7 O、LF 0.5 N 0.5 O and LF 0.7 N 0.3 The band gap values of O are 1.91, 1.82 and 1.90eV respectively, and from the results, it can be seen that doping Ni element can reduce the band gap energy of the catalyst and improve the visible light absorption, so that the catalytic material is more easily excited by visible light.
Assessment of LFO and LF by testing Electrochemical Impedance Spectroscopy (EIS) and transient photocurrent response 0.5 N 0.5 Photoelectric properties of O. FIG. 8 is LFO and LF 0.5 N 0.5 The EIS spectrum of O, the front semi-arc diameter of which represents the charge transfer resistance, shows that LFO has the largest arc diameter, indicating that the high resistance of LFO inhibits electron transfer. LF compared with LFO 0.5 N 0.5 The resistance of O is obviously reduced, and the electron transfer rate in the material can be greatly improved by the existence of Ni. LFO and LF 0.5 N 0.5 The transient photocurrent response of O is shown in fig. 9, which reflects the separation efficiency and migration rate of the photo-generated electron-hole pairs of the catalyst under light, LF 0.5 N 0.5 O has stronger photocurrent density than LFO, while LFO has certain photoresponsive capability, the doping of Ni element makes LF 0.5 N 0.5 O generates more photocurrent under photoexcitation, thereby enhancing e - /h + Separation efficiency. Thus, the incorporation of Ni in LFO can suppress e - /h + To enhance LF) 0.5 N 0.5 Catalytic activity of O.
Example 5: the patent also discloses application of the nickel-doped lanthanum-iron-perovskite in degrading antibiotics, and based on the preparation method of the nickel-doped lanthanum-iron-perovskite, the nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst to activate H 2 O 2 Degrading the antibiotic, preferably norfloxacin in this case. Specifically, the conditions of use are preferably: under an acidic environment, 1.0g/L nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst, and 15mM H is activated under the irradiation of visible light 2 O 2 Degrading norfloxacin.
Undoped and Ni-doped LaFeO prepared for evaluation and comparison 3 Is shown in H 2 O 2 And performing an oxidation test for degrading norfloxacin under the illumination condition. Degradation experiments were performed in a PerfectLight PLS-SXE300D reactor using a 300W xenon lamp as simulated visible light. The distance between the xenon lamp and the high boron silicon double-layer jacketed beaker reactor was 5cm and was equipped with circulating cooling water to prevent overheating. First, the catalyst was dispersed into a NOR solution containing 50mL (10 mg/L). The adsorption-desorption equilibrium was established by stirring with a magnetic stirrer at 400rpm for 30min before light irradiation. Then the xenon lamp is turned on, and a certain amount of H is added at the same time 2 O 2 Triggering a catalytic reaction. In the reaction process, the solution is collected by a syringe every 20min and filtered by a microporous filter membrane of 0.22 mu m. The NOR concentration was determined by spectrophotometry at 273 nm. By plotting the degradation efficiency (C t/ C 0 ) The relation between the degradation time and the photocatalytic degradation dynamics curve is obtained, wherein C 0 At an initial concentration of C t For a given time concentration.
As shown in fig. 10, in order to ensure that the catalyst and the contaminants are in sufficient contact when the adsorption reaches equilibrium, the adsorption reaction is performed for 30min in the dark, and the adsorption effect of the material in the photocatalytic reaction is eliminated, so that the material is catalyzed rather than adsorbed in the degradation experiment. After adsorption equilibration, the concentration of NOR decreased to varying degrees in the 4 sets of experiments, indicating that the catalyst can adsorb small amounts of NOR. Although it is suckedThe system is indispensable, but the degradation of pollutants mainly depends on the catalytic degradation of a catalyst, and the removal effect of adsorption on the pollutants is negligible. The removal rate of pure LFO to NOR is 49.11% in 120min, LF 0.5 N 0.5 The catalytic performance of O is highest, the NOR removal rate is 91.98%, and the next is LF 0.7 N 0.3 O (78.14%) and LF 0.3 N 0.7 O (66.0%). Experimental results show that the addition of Ni can accelerate LaFeO 3 Rate of photo Fenton-like catalysis. According to the result, selecting LF with highest catalytic efficiency 0.5 N 0.5 O material as a preferred embodiment.
In addition, the initial pH was adjusted with NaOH (0.1M) and HCl (0.1M), and the light was single, H was conducted under the same reaction conditions as in the control experiment 2 O 2 Single, light+H 2 O 2 Photo + catalyst and H 2 O 2 Degradation experiments with+ catalyst and examined pH, H 2 O 2 The concentration, the catalyst addition amount and other important factors affect the degradation efficiency of the NOR.
The pH of the solution is the most important parameter affecting the photo Fenton-like reaction, H + And OH (OH) - Directly changing the concentration of H 2 O 2 The effect of different initial pH's of 3-11 on NOR degradation was thus investigated and the results obtained are shown in FIG. 11. At ph=3, LF 0.5 N 0.5 The removal rate of O from NOR in 120min was 91.98%, and when the initial pH was adjusted to increase from 3 to 11, the degradation rate decreased with increasing pH, and the dissociation constant of NOR showed that under acidic conditions, the positively charged NOR (pK a1 =6.34,pK a2 =8.75) facilitates adsorptive contact with the catalyst. As the pH increases, OH in alkaline environments is more likely to react with OH - The reaction occurs, thereby reducing the concentration of OH and the degradation rate. Thus, an environment with an initial pH of 3.0 is chosen as the preferred embodiment.
To determine H 2 O 2 Effect of concentration on NOR degradation efficiency, at initial ph=3, H 2 O 2 LF was performed at concentrations of 5, 10, 15 and 20mM, respectively 0.5 N 0.5 Catalytic activity experiments for class O photo Fenton degradation NOR. From the slaveAs can be seen in FIG. 12, when H 2 O 2 At a concentration of 15mM, the degradation efficiency of NOR was highest, reaching 91.98%, H 2 O 2 The removal rates of NOR reached 66.50%, 84.99% and 87.46% at concentrations of 5mM, 10mM and 20mM, respectively. When the initial H 2 O 2 At too low a concentration, only a small fraction of NOR is degraded, while H 2 O 2 Has been consumed, along with H 2 O 2 The increase in concentration, the resulting high amount of OH mineralizes NOR to H 2 O and CO 2 . When H is 2 O 2 At concentrations exceeding 15mM, the degradation rate of NOR decreases because of H 2 O 2 Is an amphoteric substance which is a source of OH and a quencher, but OH radicals generated by electron holes are replaced by H 2 O 2 Consumption, formation of weak oxidation/HO 2 Thus H 2 O 2 Too high an initial concentration is detrimental to NOR degradation rate. Thus, H was selected at a concentration of 15mM 2 O 2 As a preferred embodiment.
Figure 13 shows the effect of catalyst usage on degradation efficiency. When LF (ladle furnace) 0.5 N 0.5 When the O dosage is increased from 0.5g/L to 1.0g/L, the NOR removal rate is increased from 79.44% to 91.98% in 120 min. However, when the catalyst amount is increased to 1.0g/L to 2.0g/L, degradation performance is rather degraded, and there is a possibility that excessive catalyst affects turbidity of the solution, and when the concentration of the catalyst reaches a certain concentration, particles hidden inside the catalyst cannot be illuminated by light, resulting in degradation of catalytic activity. Therefore, in combination with practical application, LF is selected 0.5 N 0.5 The optimum amount of O is 1.0g/L as a preferred embodiment.
As shown in fig. 14, the NOR removal rate was negligible only under visible light irradiation, indicating that the structurally stable NOR was not self-efficient under visible light irradiation. By using H alone 2 O 2 The degradation rate of (2) was very low, only 2.47%, indicating that H was not activated 2 O 2 It is difficult to generate active oxygen to degrade NOR. In LF 0.5 N 0.5 O/light、LF 0.5 N 0.5 O/H 2 O 2 And light/H 2 O 2 In the reaction system, the NOR removal rate after 120min9.91%, 12.57% and 39.32%, respectively. In LF 0.5 N 0.5 O (1 g/L) and H 2 O 2 In the presence of (15 mM), the initial pH was 3, and the degradation efficiency of NOR was improved to 91.98% after 120min of visible light irradiation. This is due to H 2 O 2 In the presence of LF is promoted 0.5 N 0.5 The separation of O photoelectrons and holes accelerates the formation of active free radicals on the iron-containing catalyst and the electron transfer inside the catalyst, thereby improving the photo-Fenton-like catalytic performance of the catalyst.
Example 6: based on the use of the nickel-doped lanthanum-iron-perovskite disclosed in example 5 for degrading antibiotics, preferably the nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst for activating H under irradiation of sunlight or a xenon lamp 2 O 2 Degrading the antibiotics.
FIG. 15 shows different light source pairs LFO and LF 0.5 N 0.5 The influence of the O photolysis efficiency is tested under the irradiation of sunlight and a xenon lamp, and in the test for 2 hours, the degradation rate under the irradiation of the sunlight reaches 89.09%, and the degradation rate under the irradiation of the xenon lamp reaches 91.98%. Although the natural light intensity is far lower than that of xenon lamp, the photocatalytic efficiency is only 2.89%, and the result shows that LF 0.5 N 0.5 The O photocatalyst can effectively degrade organic pollutants under natural illumination, so that potential application of the photocatalyst in natural environment is enhanced.
Example 7: based on the use of a nickel doped lanthanum iron perovskite as disclosed in example 5 for degrading an antibiotic, preferably Ciprofloxacin (CIP), enrofloxacin (ENR) or tetracycline hydrochloride (TC). Fig. 16 shows LF 0.5 N 0.5 O (1 g/L) and H 2 O 2 The degradation effect on other antibiotics in the presence of (15 mM) and under the conditions of initial pH of 3 and visible light irradiation proves that the catalyst has good degradation performance on CIP (83.40%), ENR (80.74%) and TC (87.08%). Thus, LF 0.5 N 0.5 O is used as a catalyst and has universal applicability to the removal of various antibiotic pollutants in a visible light reaction system.
In addition, the stability and sustainability of the catalyst are important indicators for evaluating the actual application of the catalyst. At the position ofUnder the same reaction conditions, LF was measured in four consecutive cycles 0.5 N 0.5 Catalytic performance of the O catalyst. From the results of fig. 17, it can be seen that the degradation rate of the catalyst on NOR from 91.98% to 77.50% was reduced from the first cycle to the fourth cycle, and the catalyst was obtained with satisfactory results although the catalytic efficiency of the prepared catalyst was reduced, indicating that the catalyst can be reused for a plurality of times, which is advantageous for practical use in wastewater. FIG. 18 is an XRD spectrum of the original catalyst and four runs, all with LF in the reusable catalyst 0.5 N 0.5 The positions of the characteristic peaks related to O are not changed obviously, which proves that LF 0.5 N 0.5 The O nanomaterial has high structural stability in catalytic cycle.
The invention adopts a sol-gel method to prepare the Ni-doped LaFeO 3 Composite material, which is used as catalyst to activate H 2 O 2 The antibiotic is degraded, the band gap energy of the catalyst can be reduced by doping Ni element, and meanwhile, the perovskite composite material can generate more photocurrent under the excitation of light by doping Ni element, so that the separation capability of carriers is enhanced, and the catalytic activity of the perovskite composite material is improved; meanwhile, the nickel-doped lanthanum-iron-perovskite composite material prepared by the method is used as a catalyst, and antibiotics can be effectively degraded under different illumination conditions, so that the potential application of the photocatalyst in natural environment is enhanced; in addition, the nickel-doped lanthanum-iron-perovskite composite material prepared by the method is used as a catalyst, has universal applicability to removal of various antibiotic pollutants in a visible light reaction system, and has higher application and popularization values.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The application of the nickel-doped lanthanum-iron-perovskite in degrading antibiotics is characterized in that the nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst to activate H 2 O 2 Degrading antibiotics, wherein the antibiotics comprise one or more of norfloxacin, ciprofloxacin, enrofloxacin or tetracycline hydrochloride, and the nickel-doped lanthanum-iron-perovskite composite material is used as a catalyst to activate H under the irradiation of sunlight or a xenon lamp 2 O 2 Degrading the antibiotic;
the preparation method of the nickel-doped lanthanum-iron-perovskite composite material comprises the following steps:
s1, laCl 3 ·7H 2 O、FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 O and citric acid are dissolved in deionized water to form a mixed solution;
s2, evaporating the water of the mixed solution to obtain wet gel, and drying the wet gel to obtain xerogel;
s3, crushing the xerogel, calcining at a high temperature of at least 400 ℃, and cooling to room temperature to obtain the nickel-doped lanthanum-iron-perovskite composite material.
2. Use of a nickel doped lanthanum iron perovskite according to claim 1 for degrading antibiotics, wherein in step S1 the LaCl 3 ·7H 2 O、FeCl 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of the mixture of O and the citric acid is 1:2.5.
3. Use of a nickel doped lanthanum iron perovskite according to claim 2 for degrading antibiotics, characterized in that in step S1 the feci 3 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is 3:7-7:3.
4. Use of a nickel doped lanthanum iron perovskite according to claim 3, characterized in that in step S1 0.02mol LaCl is used for degrading antibiotics 3 ·7H 2 O、0.01mol FeCl 3 ·7H 2 O、0.01mol Ni(NO 3 ) 2 ·6H 2 O and 0.1mol of citric acid are dissolved in 300mL of deionized water to form a mixed solution, and the mixed solution is stirred for 20-40min.
5. The use of a nickel doped lanthanum iron perovskite according to claim 1 for degrading antibiotics, characterized in that 1.0g/L of nickel doped lanthanum iron perovskite composite material is used as catalyst for activating 15mM H under irradiation of visible light in an acidic environment 2 O 2 Degrading norfloxacin.
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| CN103263943A (en) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | Preparation method of LaF3O3/SBA-15 and application |
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| KR20210155311A (en) * | 2020-06-15 | 2021-12-22 | 포항공과대학교 산학협력단 | Perovskite oxide composite catalyst, method of preparing same and water gas shift method using same |
| CN117205931A (en) * | 2023-07-28 | 2023-12-12 | 南开大学 | Copper-doped lanthanum ferrite catalyst, preparation method thereof and application thereof in nitrobenzene pollutants |
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| CN103263943A (en) * | 2013-05-14 | 2013-08-28 | 中南民族大学 | Preparation method of LaF3O3/SBA-15 and application |
| CN105642299A (en) * | 2016-02-05 | 2016-06-08 | 常州大学 | Nickel-doped lanthanum ferrite/clay nano-structure composite and preparation method and application thereof |
| KR20210155311A (en) * | 2020-06-15 | 2021-12-22 | 포항공과대학교 산학협력단 | Perovskite oxide composite catalyst, method of preparing same and water gas shift method using same |
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