CN113231068B - Perovskite material with excessive A site, preparation method and application in catalytic treatment of organic wastewater - Google Patents
Perovskite material with excessive A site, preparation method and application in catalytic treatment of organic wastewater Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 title abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 69
- 239000001301 oxygen Substances 0.000 claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 61
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 36
- 229940043267 rhodamine b Drugs 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 4
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- -1 oxygen ion Chemical class 0.000 claims description 3
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- 230000000593 degrading effect Effects 0.000 abstract description 6
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- 235000019394 potassium persulphate Nutrition 0.000 description 55
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- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 3
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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 Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an A-site excess perovskite material, a preparation method and application in catalytic treatment of organic wastewater, and belongs to the technical field of perovskite oxide catalytic materials and application. Perovskite oxide La with excess A site 1+x NiO 3‑δ Has higher material surface oxygen vacancy, and shows higher catalytic activity and efficiency for degrading organic wastewater.
Description
Technical Field
The invention relates to an A site excess perovskite material, a preparation method and application in catalytic treatment of organic wastewater, belonging to the technical field of perovskite oxide catalytic materials and application.
Background
Advanced Oxidation Processes (AOPs) play an important role in the field of sewage remediation, particularly in the process of removing recalcitrant organics in harsh aqueous environments. The organic matter is oxidized by Reactive Oxygen Species (ROS) having a high oxidation-reduction potential and decomposed into H 2 O and CO 2 For example, hydroxy(s) ((R)) • OH，E 0 = 1.9-2.7 eV), sulfate (SO 4) •- ，E 0 = 2.5-3.1 eV) and singlet oxygen ((ii) 1 O 2 And E0 = 2.2 eV). Because of the asymmetric structure of potassium Peroxydisulfate (PMS), SO can be efficiently generated by the cleavage of O-O bonds in catalyst-activated PMS 4 -and-OH radicals. However, free radicals are unstable in complex aqueous environments, such as extreme pH values and coexisting anions. Wire(s)Oxygen in the state of ( 1 O 2 ) Is an excited state of molecular oxygen, has been localized as a highly active oxidant in AOPs due to its excellent water resistance characteristics and high selectivity for organic contaminants.
However, there is still a lack of a catalyst system that can effectively activate potassium hydrogen Persulfate (PMS).
Disclosure of Invention
The invention provides a perovskite oxide La with excessive A site 1+x NiO 3-δ It has higher material surface oxygen vacancy and shows higher catalytic activity and efficiency for degrading organic wastewater.
The technical scheme is as follows:
a first object of the present invention is to provide:
a perovskite oxide having the formula: la 1+x NiO 3-δ ，0<x<0.2, delta is the content of oxygen vacancy, and delta is more than or equal to 0 and less than or equal to 1.
In one embodiment, x is preferably 0.15.
A second object of the present invention is to provide:
the perovskite oxide is prepared by a solid phase method or a sol-gel method.
In one embodiment, the preparation method is a sol-gel method comprising the steps of: according to the stoichiometric ratio, adding La (NO) 3 ) 3 •6H 2 O and Ni (NO) 3 ) 2 •6H 2 Dissolving O in deionized water, adding an ammonia water solution of EDTA and citric acid, performing a complex reaction, adding ammonia water to adjust the pH value, heating to form gel, and drying and calcining to obtain the perovskite material.
In one embodiment, EDTA: and (3) citric acid: the molar ratio of total metal ions is 1:2:1.
in one embodiment, the drying process parameters are: 180. air drying at 6 deg.C for 6 hr.
In one embodiment, the calcination process parameters are: 800. at 5 deg.C for min -1 Calcination at a temperature rising Rate of 30And 0 minute.
A third object of the present invention is to provide:
the perovskite material is used for degrading organic matters in waste water containing potassium hydrogen persulfate.
In one embodiment, the perovskite material has a concentration of 0.1 to 2g/L in wastewater, oxone has a concentration of 0.2 to 5g/L in wastewater, and the degradation process temperature is 5 to 45 ℃.
A fourth object of the present invention is to provide:
la with excess A at the increased La 1+x NiO 3-δ Use of oxygen vacancies, reduction of activation energy or activation of lattice oxygen of perovskite materials.
Advantageous effects
The invention provides perovskite material La 1+x NiO 3-δ The catalyst utilizes excessive doping of the A site, not only can form a two-phase composite interface, but also can greatly promote lattice oxygen transfer of a composite material nano interface, so that the catalyst has higher reaction activity.
L 1.15 NO not only has a special single perovskite Ruddlesden-Popper perovskite structure, but also has degradation activity on RhB (k =0.310 min) -1 ) Is LNO, L 1.1 NO and L 1.2 1.61, 1.48 and 1.24 times NO, with LNO (31.11 kjmol) -1 ) In contrast, L 1.15 Activation energy of NO (21.96 kjmol) -1 ) Lower.
Ni n+ Has a low average valence, a large specific surface area and a rich oxygen vacancy on the catalyst.
In contrast to the other catalysts, L 1.15 NO shows good stability after three continuous circulations, and the generation of active oxygen is not influenced by pH under different environmental parameters and water compositions, so that the NO has strong anti-interference capability.
Drawings
FIG. 1: (a) L is 1.15 XRD pattern of NO (wherein,. Represents La) 2 NiO 4 1-5 curves represent LNO, respectively 3 、L 1.1 NO 3 、L 1.15 NO 3 、L 1.2 NO 3 、L 2 NO 3
) (b-f) TEM and HRTEM images, (g-i) L 1+x SEM image of NO (x =0,0.15,2)
FIG. 2: (a) L is 1+x NO 3-δ Oxygen non-stoichiometric ratio (δ) of catalyst. (b) LNO and L 1.15 The oxygen vacancy profile of NO (symbol Δ represents the difference between the two simplices). Catalyst surface (c) La3d 3/2 、Ni2p 3/2 And (d) XPS spectra of O1 s.
FIG. 3: LNO and L in RhB degradation process 1.15 Comparison of adsorption characteristics of NO
FIG. 4: (a) L is a radical of an alcohol 1+x Catalytic evaluation of NO (x =0,0.1,0.15, 0.2) on RhB degradation (curves 1-6: LNO + L, respectively) 2 NO 4 Physical mixture of (A), LNO, L 1.1 NO、L 1.2 NO、L 1.15 NO、L 2 NO 4 ). (b) Different oxidizing agents, (c) different organic contaminants and (d) different temperature vs. L 1。15 Influence of the NO/PMS system (curves 1-4 at 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, respectively). (Condition: [ contaminants ]] 0 = 20 mg L -1 , [L 1+x NO] 0 = 0.2 g L -1 , [PMS] 0 = 0.8 g L -1 )
FIG. 5: l is 1+x NO (x =0,0.1,0.15, 0.2)/corresponding first order kinetics in the PMS system;
FIG. 6: (a) L is a radical of an alcohol 1.1 PMS decomposition curves in 5NO/PMS and LNO/PMS systems. (b) L in PBS solution 1.15 I-T curves for NO and LNO. (c) L in PMS solution 1.15 EIS diagrams for NO and LNO. The conditions are T =25 ℃ and [ RhB ]] 0 = 20 mg L -1 , [L 1+x NO] 0 = 0.2 g L -1 , [PMS] 0 = 0.8 g L -1
FIG. 7 is a schematic view of: (a) Different radical scavengers (CH) 3 OH, TBA and FFA) to LNO and L 1.15 Effect of RhB degradation in NO system. (b) - (c) quenching L with DMPO and TEMP 1.15 EPR spectrum of the active oxygen species of the NO/PMS system. (d) At LNO and L 1.15 Hydroxyl radical (DMPO- • OH) Strength, linear oxygen Release and RhB decolorizationA change in (c). (e) L is a radical of an alcohol 1+x CV curve of NO sample in Ar saturated 6 MKOH. (f) Measurement of L by chronoamperometry 1+x Oxygen diffusion coefficient D in NO catalyst 0 . (curves 1-5 refer to LNO, L, respectively 1.1 NO、L 1.2 NO、L 1.15 NO、L 2 NO 4 ) With the proviso that T =25 ℃, [ RhB ℃] 0 = 20 mg L -1 , [L 1+x NO] 0 = 0.2 g L -1 , [PMS] 0 = 0.8 g L -1
FIG. 8: LNO/PMS (a) and (c) and L 1.15 DMPO and TEMP Capture EPR spectra for NO/PMS systems (b) and (d)
FIG. 9: fresh and used L 1.15 XPS spectra of NO surface O1 s.
FIG. 10: l in three cycles 1.15 NO (a) RhB degradation and (b) XRD profile. (c) L is a radical of an alcohol 1.15 NO/PMS System at 10mM Cl - 、CO 3 2- 、PO 4 3- And 20mg L -1 RhB degradation curve in the presence of FA. (d) L is a radical of an alcohol 1.15 Cl with different concentrations in NO/PMS system - Effect on RhB degradation. L is a radical of an alcohol 1.15 RhB degradation curves for NO/PMS systems in (e) different pH values (f) different water matrices. With the condition of [ RhB] 0 = 20 mg L -1 , [L 1+x NO] 0 = 0.2 g L -1 , [PMS] 0 = 0.8 g L -1 , T =25 ℃
FIG. 11: rhB degradation curves in tap water, lake water and deionized water for LNO/PMS systems. Condition [ RhB] 0 = 20 ppm, [Catalyst] = 0.2 g L -1 , [PMS] = 0.8 g L -1 , T =25 ℃
Detailed Description
Synthesis of LNO perovskite catalytic material
La 1+x NiO 3-δ (x =0,0.1,0.15,0.2) was prepared by a sol-gel method. The specific method comprises the following steps: adding stoichiometric La (NO) 3 ) 3 •6H 2 O and Ni (NO) 3 ) 2 •6H 2 Dissolving O in deionized water, and then adding an ammonia water solution of EDTA and citric acid as complexing agents into the deionized water to form a transparent nitrate solution, wherein the weight ratio of EDTA: lemon (fruit of lemon)Citric acid: the molar ratio of total metal ions is 1:2:1, simultaneously reacting NH 3 ·H 2 O is added dropwise to the resulting solution to adjust the pH. The solution was then heated with vigorous stirring to evaporate the water and form a gel. Drying the concentrated gel in an oven at 18 deg.C for 6 hours to obtain a perovskite precursor, and then subjecting the precursor to a temperature of 800 deg.C for 5 deg.C min -1 Calcining for 300 minutes at the heating rate of (1) to obtain the perovskite material.
Characterization method
Determination of the nonstoichiometric oxygen ratio of the B site and Ni by Redox back titration n+ Further verified by X-ray photoelectron spectroscopy with Al-K α (XPS, PHI 5000 VersaProbe). The leached nickel ion concentration was determined by inductively coupled plasma mass spectrometry (ICP-MS, optima 7000 DV, perkin-Elmer). Electrochemical tests were performed using a CHI 760E double potentiostat in a three-electrode cell containing 0.1M phosphate buffer, the working electrode being a Rotating Disk Electrode (RDE), platinum as the counter electrode and an Ag/AgCl electrode as the reference electrode. The active species in the catalyst/PMS system was detected by a Bruker EMX-E EPR device. Wherein DMPO and TEMP are used as spin trapping agent for measuring free radical (SO) 4 -,. OH) and singlet oxygen (C) 1 O2)。
Degradation experiments were performed in the beaker, in which potassium hydrogen Persulfate (PMS) was catalytically activated with the prepared catalyst, and the results were evaluated by degrading the contaminant rhodamine B (RhB). The method comprises the following steps: 20mg of the catalyst was added to a solution containing the starting concentration of 20mgL -1 In 100mL of buffer solution. The reaction conditions are as follows: 300 rpm under water bath 298K. The water sample needed to be filtered through a 0.45 μm membrane in the experiment and the contaminant concentration was tested in a uv-vis spectrophotometer under a uv detector (λ =554 nm). The remaining solution was extracted and the solids/water separated and the resulting solution was used for ICP analysis. Using H 2 SO 4 Or NaOH adjusted the initial pH to 3, 5, 8 and 10. By adding Na 2 CO 3 、NaCl、Na 3 PO 4 The influence of coexisting anions was examined. All experiments were repeated at least three times. KI/NaHCO is adopted 3 The method comprises the following steps of (1),the concentration of oxone was determined using a UV-Vis spectrophotometer. To investigate L 1.15 The recyclability of NO, the reaction catalyst was filtered and washed with deionized water and ethanol, and the washed catalyst was dried to perform the degradation experiment again.
Mechanism exploration determination process: l was measured by quenching experiment using Methanol (MEOH), t-butanol (TBA) and furfural (FFA) as quenchers 1.15 Reactive Oxygen Species (ROS) in NO/PMS. Further, after argon bubbling for half an hour in 6M KOH solution, the oxygen diffusion modulus (D) was calculated from the CV curve 0 ). CV curve is taken as L 1+x NO modified working electrode, carbon rod as counter electrode and Hg/HgO as reference electrode, and 20mVs −1 Is measured. Obtaining i vs t by chronoamperometry -1/2 The curve was plotted and the anode potential was calculated as about 50mV higher from the average potential between oxygen intercalation/delamination peaks. According to the formula λ = a (D) 0 t) −1/2 Calculating D in the Crystal 0 Wherein t is −1/2 Is the value of i vs t at t =0 −1/2 The intercept of the curve, λ, is set as a shape factor of 2, which is between 1.77 (sphere) and 2.26 (cube), the particle radius a being given by the equation S = 6/(2 a ρ).
Prepared L 1+x Characterization of NO perovskite materials
Nanocomposite L 1+x The crystal structure and purity of NO is shown by a of XRD pattern 1. LaNiO 3 The diffraction peak of (LNO) corresponded to cubic LNO single perovskite (JCPDS No. 33-0711), indicating a pure perovskite structure. Compared with LNO perovskite phase, L 1.15 NO and L 1.2 NO is composed of LNO and L 2 NO 4 Two-phase composite of composition, illustrating La excess L 1+x Mixed nature of NO samples. Meanwhile, L in b-f of FIG. 1 1.15 TEM and HRTEM images of NO show a spacing of 0.287nm with L 2 NO 4 The (113) plane of (2) was correlated with the XRD analysis result. SEM images of g-h of FIG. 1 show that L 1+x The particle size of the oxides of the NO series (x =0,0.1,0.15, 0.2) is similar, ranging from 100 to 200nm, the ratio L 2 NO 4 (300 nm) is small. L is 1+x The specific surface areas of NO (x =0,0.1,0.15,0.2) were 5.363 m, respectively 2 g -1 ，5.843 m 2 g -1 ，6.721 m 2 g -1 ，5.038 m 2 g -1 . And L is 2 NO 4 It is liable to agglomerate (i of fig. 1), which is the reason for its high surface energy, and the catalyst is agglomerated by the surface tension, and the active center is less exposed, resulting in a decrease in catalytic activity. The oxidation state of the B-site metal in the catalyst was obtained from the non-stoichiometric ratio of oxygen, and in a of FIG. 2, LNO was confirmed by iodometry 3-δ And L 1.15 NO 3-δ δ =0.22 indicates L 1.15 NO presents surface oxygen vacancies larger than LNO (delta = 0.079) and L 1.1 NO (δ = 0.195), indicating that the redistribution of oxygen vacancies plays an important role at the oxide interface. Further detection of LNO and L with solid-state EPR 1.15 Oxygen vacancy density of NO, LNO and L were detected at g =2.05 1.15 Characteristic EPR signal of electron capture sites on oxygen vacancies in NO. L is 1.15 Higher EPR signal intensity for NO, indicating L 1.15 The degree of oxygen vacancy of NO is greater than that of LNO, L is presumed 1+x The final properties of the NO/PMS system may be closely related to oxygen vacancies and lattice oxygen.
The surface electron state of the catalyst was analyzed by X-ray photoelectron spectroscopy (XPS), in which Ni 2 is present p3/2 And La3 d3/2 Overlap in binding energy (c of FIG. 2), and the strongest Ni 2 p3/2 With satellite peaks. The O1s spectrum is convolved as shown in d of fig. 2. At 533.3ev (O) IV ) The peak at (a) is related to adsorbed oxygen, which is mainly present on the catalyst surface. At 528.47ev (OI) and 529.35ev (O) II ) The peaks at (a) are due to lattice oxygen and oxygen vacancies, respectively. Further, the adsorbed oxygen and hydroxyl groups formed a third peak (O) at 531.47ev III ). The relative density of oxygen vacancies is determined by the relative intensity ratio of the peaks (RIR = O) II /O I ) And (6) estimating. The results show that L 1.15 The concentration of oxygen vacancies at NO (RIR = 0.619) was greater than the concentration of oxygen vacancies at LNO (RIR = 0.549), which is better consistent with the solid state EPR analysis and oxygen non-stoichiometric ratio (δ) results described above. This enhanced oxygen vacancy is created by the presence of a two-phase nano-interface, which may in turn have a potential impact on the activation mechanism.
L 1+x NO 3-δ Performance of A site excess on perovskite oxides in PMS heterogeneous catalytic activation
In a potassium hydrogen Persulfate (PMS) activation system, the influence of the composite material on the catalytic performance of the LNO perovskite oxide is investigated by adopting different pollutant degradation efficiencies. At L 1.15 In the presence of NO and LNO alone, only a small amount of RhB is decomposed (fig. 3), indicating that the adsorption capacity of the catalyst for RhB is poor. Similar results were obtained with PMS without catalyst, indicating that the self-decomposition of PMS is less efficient at degrading contaminants. In contrast, when the catalyst and PMS were present (a of FIG. 4), the degradation of RhB was significantly enhanced, and L was 1.15 The NO/PMS system shows excellent RhB degradation performance, reaches 97% of removal rate within 10min, and has the following catalytic activity sequence: l is a radical of an alcohol 1.15 NO 3 > L 1.2 NO 3 > LNO 3 > L 1.1 NO 3 > L 2 NO 4 The catalyst is shown to be capable of heterogeneously activating PMS to oxidize RhB. L is 1.15 The improvement in NO performance is due in part to the increase in specific surface area, the increase in oxygen vacancies, and the low price of Ni ions. At the same time, L 1+x The reaction on NO follows the first order kinetic equation:
L 1.15 k of NO-activated PMS 1 The highest value (0.310 min) -1 ) And secondly is L 1.1 NO-activated PMS (0.209 min) -1 ) LNO activated PMS (0.192 min) -1 ) And L 1.2 NO-activated PMS (0.250 min) -1 ). Furthermore, to better analyze L 1.15 The catalytic performance of NO was tested with different oxidant activations and pollutants. From b of FIG. 4, it can be seen that potassium Persulfate (PDS) can be activated and completely degrade RhB within about 100 min, while other oxidants such as H 2 O 2 Its O-O bond energy is much higher than that in PDS, indicating H 2 O 2 Catalytic activation is likewise hindered. In addition, c of FIG. 4 shows the end energies of four typical contaminantsQuilt L 1.15 Degrading the NO/PMS system. Phenol (PE) and Atrazine (ATZ) are relatively slow to degrade compared to RhB and Sulfamethoxazole (SMX) due to their stable structure and high decomposition difficulty. To evaluate L 1.15 The thermodynamic effect of the NO nanocomposite catalyst was followed by temperature testing. The first order kinetic fitting constant increased from 0.310 to 0.491 min as the temperature increased from 25 ℃ to 45 ℃ −1 Then, the activation energy (E.alpha.) representing the minimum energy required for the reaction was calculated according to the Arrhenius equation (d in FIG. 4). L is 1.15 The estimate of E.alpha.for NO was 21.9 KJ mol −1 E α (31.1 KJ mol) lower than LNO −1 ) Indicating that it has excellent activity.
In addition, from L, it was evaluated using ICP-AES 1+x The metal ions leached from the surface of the NO perovskite oxide into the water sample are used for testing the toxicity of the NO perovskite oxide in the practical wastewater application.
TABLE 1 LNO, L determined by ICP at the end of the RhB degradation experiment at 25 deg.C 1.15 Leached nickel ion concentration of NO
| Sample(s) | Ni(mg/L) |
| LNO | 0.542 |
| L 1.15 NO | 0.941 |
LNO, L after the degradation reaction of RhB are listed in Table 1 1.15 Leaching concentration of metal ions of nickel ions in NO. The results show that LNO and L are in the filtrate 1.15 The nickel ion concentration of NO is less than 1mgL -1 . But is actually processedOf these, similar nickel ion leachables have little effect on the level of heavy metal contamination. The above results indicate that the A site is over-doped with L 1+x NO is a good catalyst for PMS activation.
Due to L 1.15 NO has remarkable catalytic activity on PMS activation, and the mechanism process of NO is further researched. A of fig. 6 shows the close relationship between PMS composition and reaction rate. In the absence of PMS or catalyst (L) 1.15 NO), rhB was hardly degraded (fig. 3), indicating that RhB was mainly at L 1.15 Degradation in PMS activation of NO surface. In order to better study the catalytic mechanism, the charge transfer capacity of the catalyst was examined. As shown in b of FIG. 6, PMS was added to the electrolyzer at 150s, a momentarily elevated current was detected, probably because of PMS and Ni 2+ Or electron transfer between lattice oxygens. However, the current intensity is obviously reduced after the organic matter is added, which is probably caused by that the absorbed RhB occupies some active centers on the surface of the catalyst, and the activity of PMS is reduced. L is a radical of an alcohol 1.15 NO has strong interaction with PMS and organic matters, can effectively activate PMS, and the result is L in EIS diagram 1.15 The semicircular diameter of NO is smaller than that of LNO and is consistent.
In addition, active oxygen Species (SO) associated with PMS activation were studied by quenching experiments and EPR analysis 4 •- ， • OH， 1 O 2 ). Methanol and tert-butanol are usually used as • OH and SO 4 •- The quencher of (1), L shown in a of FIG. 7 1.15 In the NO/PMS system, the quenching effect of methanol on RhB degradation is higher (49.3%) than that of tert-butyl alcohol (39.0%), showing SO 4 •- And • co-presence of OH, whereas DMPO-SO is generated in b-c of FIG. 7 4 •- And DMPO- • OH signals, confirming their tendency to generate ROS in LNO/PMS. The free radical process is liable to occur on the catalyst with higher redox reaction activity, and the positive process is as follows:
Ni 2+ + HSO 5 - → Ni 3+ + SO 4 •- + OH - (1)
Ni 3+ + HSO 5 - → Ni 2+ + SO 4 •- + H + (2)
SO 4 •- + H 2 O → SO 4 2- + H + + • OH (3)
however, non-radically active species also have an irreplaceable role in the reaction. As shown in a of FIG. 7, towards L 1.15 Quenching can be achieved by adding the catalyst into a NO/PMS reaction system 1 O 2 The degradation of RhB was significantly inhibited by 84.8%. Meanwhile, the intensity of 1 1 O 2 Characteristic peaks were detected, the number of which increased with time (fig. 8). In combination with the quenching analysis described above, we found that 1 O 2 Is proportional to the increase in catalytic ability, indicating that 1 O 2 Is the main active oxygen species in redox reactions. It is noted that L in b of FIG. 2 1.15 NO has a high number of surface oxygen Vacancies (VO) •• ) And PMS activation, however LNO due to limited surface oxygen vacancyThe bit has a lower PMS activation efficiency. VO (volatile organic compound) •• Is an effective oxygen ion conductor which passes through L 1+x NO 3 Perovskite control 1 O 2 And (4) generating. Lattice oxygen participation 1 O 2 The mechanism of formation is as follows:
wherein V O •• Is an oxygen vacancy, O 2- Oxygen ion of lattice representing normal position, O * Is active oxygen. Some lattice oxygen atoms in the catalyst may be released and converted to O * To support the occurrence of new oxygen vacancies in the crystal lattice. Once PMS is dispersed in the aqueous solution, O * Is easily generated by electron transfer 1 O 2 . At the same time, L after use was analyzed by XPS spectroscopy 1.15 The RIR value of NO increases (fig. 9), which means that the relative content of lattice oxygen decreases, and the occurrence of lattice oxygen participation in the reaction is laterally confirmed. The diffusion rate of lattice oxygen was measured using electrochemical tests to demonstrate the reaction mechanism described above. The occurrence of the redox peak is shown in e of FIG. 7, which indicates that oxygen is in the accessible crystal lattice vacancy (V) O •• ) And can be represented by the formula:
La 1+x NiO 3-δ + 2σOH - ↔ La 1+x NiO 3-δ+σ + σH 2 O + 2σe -
in the formula, sigma represents V O •• Occupancy, the nernst equation, is typically associated with pseudo capacitive intercalation processes. It is clear that the order of enhancement of the catalytic activity coincides with the tendency of intercalation of the lattice oxygen (e of FIG. 7), in particular L 1.15 NO exhibits superior current density in reasonable intercalation areas. Thereafter, oxygen ions are in L 1+x The diffusion coefficient in NO is described as the tendency of lattice oxygen to participate and migrate (f of fig. 7). Calculated L 1.15 D of NO 0 Modulus of 7.076X 10 −11 cm 2 s −1 Is superior to other catalysts in thatThe sequence is as follows: l is a radical of an alcohol 1.15 NO > L 1.2 NO (5.007× 10 −11 cm 2 s −1 ) > LNO (4.480×10 −11 cm 2 s −1 ) > L 1.1 NO (4.389×10 −11 cm 2 s −1 ) > L 2 NO 4 (5.007×10 −11 cm 2 s −1 ). This is consistent with the increase in intrinsic activity resulting from the increase in Lattice Oxygen Participation (LOPC) in redox reactions. L is a radical of an alcohol 1.15 NO not only has the highest LOPC, but also shows a strong tendency to oxygen delamination, i.e., la 0.3 Sr 0.7 CoO 3 Inert lattice O in (LSC) phase 2 The species also readily convert to active lattice O within the crystal and can be released. This is due to the in situ growth of Co on the LSC perovskite 3 O 4 The phases strongly interact with the bulk through enhanced electron transfer at the interface, which promotes the activation of lattice oxygen at the surface of the LSC phase by interfacial synergy. And L is 1.15 NO 3 L in composite materials 2 NO 4 Has a large amount of interstitial oxygen and high oxygen ion mobility, and L is generated while lattice oxygen is consumed in the reaction 2 NO 4 L is caused by the migration and activation of inert lattice oxygen species which continuously provide active oxygen for the reaction 1.15 Increase in oxygen delamination current density in NO. These results indicate that the increased oxygen participation of the crystal lattice contributes to the generation of large quantities 1 O 2 Thereby improving the catalytic activity.
L in the present invention 1.15 NO is used as a high-efficiency catalyst, and has good stability for activating PMS to degrade RhB. The catalyst was subjected to three consecutive cycles without deactivation of the catalytic performance, without even reduction of its performance, and the XRD patterns showed no significant change in structure between the used and the freshly prepared catalysts (a-b of fig. 10). To understand L 1.15 The application of NO in actual wastewater is carried out by adding various inorganic coexisting anions (Cl) - 、CO 3 2- 、PO 4 3- ) And humic acid (FA) for L 1.15 The influence of the application process of NO in actual wastewater was examined. From FIG. 10c can show that Cl - With slight inhibitory effect, figure 10 d also shows increased Cl - The concentration still slightly inhibited RhB degradation due to Cl • (2.47 V)、Cl 2 - (2.0 V)、ClOH •- (1.5V-1.8V) has an oxidation-reduction potential lower than that of SO 4 •- . And CO 3 2- 、PO 4 3- Has obvious inhibiting effect on the degradation of RhB in solution. This is because of SO 4 •- First, the reaction is carried out by reacting with CO as shown in the following formula 3 2- 、PO 4 3- Reacting and then forming a radical having a lower redox potential, such as PO, in the system 4 •- 、CO 3 •- Resulting in a decrease in RhB degradation efficiency.
SO
4
•-
+ Cl
-
→ Cl
•
+ SO
4
2-
OH
•
+ Cl
-
→ ClOH
•-
ClOH
•-
+ Cl
-
→ Cl
2
-
+ OH
-
SO
4
•-
+ PO
4
3-
→ PO
4
•-
+ SO
4
2-
SO
4
•-
+ CO
3
2-
→ CO
3
•-
+ SO
4
2-
OH
•
+ CO
3
2-
→ CO
3
•-
+ OH
-
Then 0.1M H is used 2 SO 4 And NaOH to adjust the pH of the wastewater to 3, 5, 8 and 10 at L 1.15 The pollutant decomposition experiment was performed in a NO/PMS system (e of FIG. 10). The results show that the degradation rate of RhB is almost the same as without pH control, indicating that the catalyst can be applied over a wide pH range of 3 to 10. Finally, lake water, tap water and deionized water are respectively adopted to prepare the initial concentration of 20mg L -1 In FIG. 10 f and FIG. 11, it can be seen that the different water bases are at L 1.15 The effect on RhB degradation in NO/PMS and LNO/PMS systems, the results show that deionized water is used as a water substrate in L 1.15 RhB can be completely degraded in a NO/PMS system within 20min, and the degradation rates of lake water and tap water reach 91% and 96% respectively. The degradation rate is slowed down with the sequence of deionized water, tap water, lake water, as can be seen from c of fig. 10, this differential result may be caused by anionic interactions in the water, especially phosphates and carbonates.
Claims (1)
1. Lattice oxygen O consumption 2- And generate 1 O 2 The method is characterized by comprising the following steps:
la 1+0.15 NiO 3-δ Adding perovskite material and potassium hydrogen persulfate into waste water containing organic matter, delta is oxygen vacancy content, consuming lattice oxygen ion O 2- And generate 1 O 2 (ii) a The concentration of the perovskite material in the wastewater is 0.1-2g/L, the concentration of the potassium hydrogen persulfate in the wastewater is 0.2-5g/L, and the process temperature is 5-45 ℃;
the La 1+x NiO 3-δ The preparation method of the perovskite material comprises the following steps: according to the stoichiometric ratio, adding La (NO) 3 ) 3 •6H 2 O and Ni (NO) 3 ) 2 •6H 2 Dissolving O in deionized water, adding an ammonia water solution of EDTA and citric acid, performing a complex reaction, adding ammonia water to adjust the pH, heating to form gel, and drying and calcining to obtain a perovskite material;
EDTA: and (3) citric acid: the molar ratio of total metal ions is 1:2:1;
the drying process parameters are: 180. drying in air at the temperature of 6 ℃ for 6 hours;
the parameters of the calcination process are as follows: 800. at 5 deg.C for min -1 Calcining for 300 minutes at the temperature rising rate;
the organic matter is rhodamine B.
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| KR20180125266A (en) * | 2017-05-15 | 2018-11-23 | 한국과학기술원 | Perovskite oxide catalyst having improved oxygen catalytic activity and method thereof |
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| Nonstoichiometric perovskite for enhanced catalytic oxidation through excess A-site cation;Ximu Li，et al.;《Chemical Engineering Science》;20200227;第219卷;正文第2.1节、第3.2-3.3节 * |
| Promoted peroxymonosulfate activation into singlet oxygen over perovskite for ofloxacin degradation by controlling the oxygen defect concentration;Panpan Gao，et al.;《Chemical Engineering Journal》;20181124;第359卷;第2.4节、第3.2节、图3 * |
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