CN115722229B - Bimetallic oxide nano material and preparation method and application thereof - Google Patents
Bimetallic oxide nano material and preparation method and application thereof Download PDFInfo
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Classifications
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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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Abstract
The invention discloses a bimetal oxide nano material and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, dissolving nickel salt in a mixed solution of N, N-dimethylformamide and ethylene glycol, then adding zinc salt, stirring at room temperature, then adding terephthalic acid, and continuously stirring until the materials are fully and uniformly mixed; s2, transferring the solution obtained in the step S1 into a polytetrafluoroethylene reaction kettle liner, sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve in an oven, performing hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and vacuum drying to obtain a precursor; and S3, performing heat treatment on the precursor to obtain the NiO-ZnO nano material with the yolk/shell structure. The NiO-ZnO composite material with the yolk/shell structure is obtained by a one-step hydrothermal method, has excellent catalytic performance, and can be used as a catalyst for treating various organic wastewater and repairing polluted water environment.
Description
Technical Field
The invention belongs to the crossing field of nano materials and advanced oxidation technology, and particularly relates to a bimetallic oxide nano material with a yolk/shell structure, and a preparation method and application thereof.
Background
Advanced oxidation technology based on Peroxomonosulphate (PMS) can be applied to the treatment and environmental remediation of a variety of refractory wastewater. The technology can generate sulfate radical (SO) in situ through the reaction of the catalyst and PMS oxidant 4 ·- ) Hydroxy radical · OH, singlet oxygen 1 O 2 ) The active species realizes the efficient oxidative decomposition of toxic refractory pollutants in water. However, various inorganic ions, humus and other soluble organic matters in water are easy to react with free radicals to cause ineffective consumption, so that the removal efficiency of the traditional process on target pollutants is remarkably reduced, and the treatment cost is increased. Compared with the prior art, the advanced oxidation process based on the adsorbed free radical has higher utilization efficiency of the oxidant because the adsorbable pollutant reacts on the surface of the catalyst, and has obvious advantages in practical water treatment application.
The choice and design of the catalyst is particularly critical to the advanced oxidation technology of PMS. The transition metal oxide has the advantages of low cost, environmental protection, flexible and adjustable properties and the like, is widely used as a Fenton-like catalyst, but is mainly concentrated on a catalytic reaction system of free radicals. Catalysts that have been reported to achieve the adsorbed free radical oxidation pathway include iron oxides, cobalt sulfides, and the like. There have been few studies to find that bimetallic oxides exhibit superior catalytic activity over single metal oxide catalysts. For example, niO-ZnO heterojunction composite catalysts are used to activate PMS while degrading contaminants via free radical and adsorbed free radical pathways, which are significantly better in catalytic activity than NiO and ZnO alone. However, the preparation process of the NiO-ZnO heterojunction catalyst is complex, and the NiO-ZnO composite material is usually generated by synthesizing ZnO with a hollow sphere structure firstly and then performing a secondary hydrothermal reaction, or the NiO-modified ZnO micro-flower structure composite material is generated by redispersing flower-shaped ZnO particles in nickel nitrate solution. In addition, the existing NiO-ZnO heterojunction catalyst has the problems of low activity, metal ion dissolution and the like (Ni in the reaction process) 2+ And Zn 2+ The dissolution amounts are respectively up to 0.3mg/L and 13mg/L, thereby greatly reducing the recycling stability of the water-soluble polymer.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the defects of complex operation, high energy consumption, poor activity of the synthesized catalyst and the like of the traditional NiO-ZnO two-step synthesis method, the invention provides a novel preparation method of a bimetallic oxide nano material with a yolk/shell structure, optimizes the structure and performance of the bimetallic oxide nano material, and can be used as a catalyst for treating various organic wastewater and repairing polluted water environment. The NiO-ZnO composite material with the yolk/shell structure is obtained by a one-step hydrothermal method, the mesoporous shell layer of the nano-reactor with the yolk/shell structure is favorable for rapid diffusion of reactant molecules, the concentration of reactants and free radicals in an internal cavity can be improved through a finite field effect, and the nano-reactor is expected to provide power for oxidation of organic pollutants such as 4-chlorophenol.
The technical scheme of the invention is as follows:
the invention relates to a preparation method of a bimetallic oxide nano material, which comprises the following steps:
s1, dissolving nickel salt in a mixed solution of N, N-dimethylformamide and ethylene glycol, then adding zinc salt, stirring at room temperature, then adding terephthalic acid, and continuously stirring until the materials are fully and uniformly mixed;
s2, transferring the solution obtained in the step S1 into a polytetrafluoroethylene reaction kettle liner, sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve in an oven, performing hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and vacuum drying to obtain a precursor;
and S3, performing heat treatment on the precursor to obtain the NiO-ZnO nano material.
Preferably, the mass ratio of the nickel salt to the zinc salt is 1:1 to 1:0.7.
Preferably, the nickel salt is Ni (NO 3 ) 2 ·6H 2 O, the zinc salt is Zn (NO 3 ) 2 ·6H 2 O。
Preferably, in step S1, the volume ratio of N, N-Dimethylformamide (DMF) to ethylene glycol is from 7:5 to 9:5; the mass of terephthalic acid accounts for 55-65% of the mass of the nickel salt.
Preferably, in the step S2, the temperature of the hydrothermal reaction is 140-160 ℃ and the time is 5.5-6.5 h.
Preferably, in step S2, after cooling to room temperature, the resulting product is centrifuged and washed three times with N, N-Dimethylformamide (DMF) and absolute ethanol.
Preferably, in the step S2, the temperature of vacuum drying is 60-80 ℃ and the time is 8-12 h.
Preferably, in step S3, the conditions of the heat treatment are: the precursor is kept at 450-550 ℃ for 20-30 min, and the heating rate is controlled at 2 ℃/min.
The invention also relates to a bimetallic oxide nano material which is prepared by adopting the preparation method and has a yolk/shell structure, and a 200-300 nm gap exists between a core and a shell.
The invention also relates to application of the bimetal oxide nano material in activating PMS and degrading organic pollutants in organic wastewater. Further preferably, the organic pollutant in the organic wastewater can be at least one of 4-chlorophenol (4-CP), bisphenol A (BPA), sulfonamide (SA) and rhodamine B (RhB), the concentration of the organic pollutant in the organic wastewater is 5-20 mg/L, the addition amount of the bimetallic oxide nano material in each liter of the organic wastewater is 0.05-0.2 g/L, and the addition amount of PMS is 0.04-0.1 g/L.
The beneficial effects of the invention are as follows:
(1) According to the invention, the NiO-ZnO bimetallic oxide nano material with the yolk/shell structure is directly synthesized by adopting a one-step hydrothermal method, so that the synthesis process is greatly simplified, metal salts are co-dissolved in the mixed solution of N, N-dimethylformamide and ethylene glycol, and the NiO-ZnO oxide with the yolk/shell structure is formed after centrifugal calcination without any template.
(2) The NiO-ZnO bimetallic oxide nano material prepared by the invention has a unique yolk/shell structure, and the yolk/shell structure remarkably enhances the catalytic degradation efficiency. The porous shell layer can protect the wrapped catalyst from the interference of the severe environment in the solution, and the limited cavity environment generates instantaneous high-concentration SO 4 · -、 · OH provides driving force for promoting the catalytic oxidation of organic pollutants such as 4-CP and the like, which also implies that the multifunctional NiO-ZnO yolk/shell nano-reactor can bring great expandability so as to enhance the catalysis of pollutants in various environmentsAnd (5) chemical degradation.
(3) The NiO-ZnO bimetallic oxide nano material obtained by the invention realizes the improvement of the activity of the NiO-ZnO catalyst, and simultaneously the Ni in the reaction system 2+ And Zn 2+ The dissolution concentration is 0.02mg/L and 0.8mg/L, and the ion dissolution amount is greatly reduced.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
fig. 1: SEM and TEM images of the yolk/shell NiO-ZnO nanomaterial of example 1;
fig. 2: XRD pattern of the yolk/shell NiO-ZnO nanomaterial of example 1;
fig. 3: the yolk/shell NiO-ZnO nanomaterial of example 1 activates PMS degradation 4-CP performance;
fig. 4: the yolk/shell NiO-ZnO nanomaterial of example 1 was changed in degradation performance to 4-CP after 4 cycles of use;
fig. 5: the yolk/shell NiO-ZnO nanomaterial of example 1 activates PMS to degrade a variety of contaminants;
fig. 6: the yolk/shell NiO-ZnO nanomaterial of example 1 activates PMS degradation 4-CP performance in different water environments;
fig. 7: the yolk/shell NiO-ZnO nanomaterial of example 1 activates ion elution concentration in PMS systems.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Example 1 preparation of NiO-ZnO bimetallic oxide nanomaterial
1. 0.25g of Ni (NO 3 ) 2 ·6H 2 O was dissolved in a mixture of 40mL of N, N-dimethylformamide and 25mL of ethylene glycol, and after complete dissolution, 0.25g of Zn (NO) was added 3 ) 2 ·6H 2 O, stirring at room temperatureAfter half an hour of stirring, 0.15g of terephthalic acid was added and stirring was continued for 1 hour until thoroughly and uniformly mixed.
2. Transferring the bright green solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle liner with the volume of 100mL, sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve in an oven, programming to be heated to 150 ℃, performing hydrothermal reaction for 6 hours, and then naturally cooling and taking out; the resulting green precipitate was centrifuged, washed three times with DMF and absolute ethanol, and dried in vacuo at 60 ℃ for 12h to give the bright green precursor.
3. And (3) keeping the precursor obtained in the step (2) at 500 ℃ for 20 minutes, and performing heat treatment under the condition of controlling the heating rate to be 2 ℃/min to obtain the black NiO-ZnO nano material.
Comparative example 1 preparation of NiO Material
The preparation conditions were the same as in example 1, except that Zn (NO) was not added in step (1) 3 ) 2 ·6H 2 O, adding Ni (NO) alone 3 ) 2 ·6H 2 O。
Comparative example 2 preparation of ZnO Material
The same conditions as in example 1, except that Ni (NO) was not added in step (1) 3 ) 2 ·6H 2 O, adding Zn (NO) 3 ) 2 ·6H 2 O。
Characterization analysis was performed on the NiO-ZnO bimetallic oxide nanomaterial synthesized in example 1:
characterization of the morphology and structure of the materials, namely, scanning Electron Microscope (SEM) and X-ray diffraction (XRD) characterization after the materials are ground uniformly. As shown in FIG. 1, SEM image shows that NiO-ZnO has the morphology of yolk shell microspheres with diameters of 2-3 μm, and hard yolk microspheres and thin shells can be clearly observed in the ruptured NiO-ZnO microspheres; TEM images show that a 200-300 nm gap exists between the shell and the core, indicating the formation of a cavity structure; as shown in fig. 2, XRD diffraction spectrum of NiO-ZnO bi-metal oxide nanomaterial demonstrated the presence of NiO, znO two phases.
Example 2 application of removing 4-CP in Water
2mg of NiO-ZnO nanoparticles were dissolved in 20mL of 10 mg/L4-CP solution and sonicated at room temperatureAfter 5min, stirring is continued for 10min to ensure that the NiO-ZnO reaches adsorption equilibrium, 40 mu L of 25g/L PMS stock solution is added to initiate reaction, and the degradation rate curve of 4-CP in the corresponding NiO-ZnO/PMS system is shown in figure 3. The PMS system in FIG. 3 represents the removal efficiency of 4-CP when PMS alone exists, the NiO-ZnO system represents the removal efficiency of 4-CP when NiO-ZnO alone exists, the NiO/PMS system and the ZnO/PMS system represent the removal effect of 4-CP when NiO and ZnO coexist with PMS, and the NiO+ZnO/PMS system represents the removal effect of 4-CP when NiO, znO and PMS coexist. As shown in fig. 3, when either blank PMS or NiO-ZnO was dosed alone, only 4% of 4-CP was degraded, indicating that both the intrinsic oxidation capacity of PMS and the adsorption capacity of NiO-ZnO were negligible. However, when NiO-ZnO and PMS are used simultaneously, 4-CP in the NiO-ZnO/PMS system is completely removed within 10 minutes, the removal rate is obviously higher than that of a blank NiO/PMS system and a blank ZnO/PMS system, and the synergy between Ni and Zn elements and the driving force for activating the PMS are disclosed. Meanwhile, ni in a NiO-ZnO/PMS system after reaction is detected 2+ And Zn 2+ The dissolution concentration is 0.02mg/L and 0.8mg/L respectively, which solves the problem of Ni in the prior art 2+ And Zn 2+ Ion elution problem (fig. 7).
Catalytic reaction pathway analysis: ethanol and tertiary butanol are selected as free radical capturing agents to be added into a NiO-ZnO/PMS reaction system, and the degradation of 4-CP cannot be inhibited, so that the existence of free radicals in a bulk solution is eliminated. Phenol is selected as a quencher for surface-bound free radicals, and the degradation performance is almost 100% inhibited. In the process of SO 4 · -、 · In the OH probe experiments, the degradation of benzoic acid and methylene blue probe contaminants was detected, which can fully demonstrate the presence of surface bound free radicals. Meanwhile, when an electron paramagnetic resonance spectrum (EPR) test is carried out, the release of surface-bound free radicals is promoted by adding sodium fluoride, signals of the free radicals are captured in the solution, and the mechanism of degrading the 4-CP by the system is verified to be the surface-bound free radicals again.
Example 3 cycle stability of yolk/Shell NiO-ZnO double metal oxide nanomaterial
The NiO-ZnO bimetallic oxide nanomaterial of example 1 was reused for contaminant-degrading catalyst materials, and specific treatment methods for removing 4-CP from water were consistent with example 2, and after each experimental reaction, the catalyst was collected by centrifugation and washed with deionized water, and the above steps were repeated for four cycles of 20 minutes each. As shown in fig. 4, the efficiency of degrading 4-CP by the yolk/shell NiO-ZnO nanomaterial was still as high as 95% in the first four cycles. After drying the material collected after the fourth cycle, the catalyst was recovered in catalytic performance by calcination to remove the residue of the surface contaminant intermediate, repeating the above experiment. Thus, the catalyst exhibits excellent cycle stability in activating PMS to degrade organic contaminants.
Example 4 yolk/shell NiO-ZnO/PMS System for actual Water sample and multiple contaminant treatment
The yolk/shell NiO-ZnO/PMS bimetal oxide nanomaterial obtained in example 1 was added to a solution to be treated with different contaminants, wherein the concentrations of the contaminants such as catalyst, PMS and 4-CP were kept the same as in example 2. FIG. 5 is a graph showing degradation rate curves for different contaminants in a NiO-ZnO/PMS system. Through tests, the NiO-ZnO/PMS system constructed by the invention can completely remove different organic pollutants (such as 4-CP, BPA, SA, rhB) within 20 minutes.
Deionized water, tap water and lake water were selected respectively for simulation of actual water environment, specifically, lake water samples (total organic carbon concentration of 33 mg/L) and tap water samples (total organic carbon concentration of 20 mg/L) were taken respectively, deionized water, wherein the concentrations of catalyst, PMS and 4-CP were kept consistent with those in example 2. FIG. 6 is a graph showing the degradation rate of 4-CP in the presence of different water samples as reaction medium, wherein deionin water represents deionized water sample, tap water represents Tap water sample, lake water represents Lake water sample, and as can be seen from FIG. 6, niO-ZnO/PMS system can completely degrade 4-CP in 25min under different water quality conditions, thus proving that the system has good environmental applicability and water treatment application prospect.
The yolk/shell NiO-ZnO bimetallic nanomaterial prepared by the invention has excellent catalytic performance, and is mainly due to the synergistic effect of Ni and Zn elements and the dual synergistic effect of yolk and shell. (1) The activation effect of the NiO-ZnO bimetallic oxide on PMS is far better than that of blank NiO and ZnO, and the strong interaction of Ni and Zn ensures the catalytic activity and the catalytic stability of the NiO-ZnO bimetallic oxide (figure 3). (2) The design of the yolk/shell structure shows the potential of NiO-ZnO nanoreactors for environmental remediation. The yolk/shell structured NiO-ZnO heterojunction catalyst achieved 100% degradation of 10mg/L bisphenol A within 10 minutes (FIG. 5). The porous shell layer allows the free entry of small molecule reactants and protects the encapsulated catalyst from the harsh components of chloride and nitrate ions in the solution, even if the active sites of the outer shell layer are occupied, the catalytic sites of the internal cavity remain active. Advantageously, the cavity between the yolk and the shell provides a reactive microenvironment such that a transiently high concentration of SO 4 ·- 、 · OH and 4-CP are limited in limited space, and the limiting field effect provides driving force for promoting 4-CP catalytic oxidation.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (11)
1. The application of the bimetal oxide nano material in activating PMS to degrade organic pollutants in organic wastewater, and the preparation method of the bimetal oxide nano material comprises the following steps:
s1, dissolving nickel salt in a mixed solution of N, N-dimethylformamide and ethylene glycol, then adding zinc salt, stirring at room temperature, then adding terephthalic acid, and continuously stirring until the materials are fully and uniformly mixed;
s2, transferring the solution obtained in the step S1 into a polytetrafluoroethylene reaction kettle liner, sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve in an oven, performing hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and vacuum drying to obtain a precursor;
and S3, performing heat treatment on the precursor to obtain the NiO-ZnO nano material.
2. The use according to claim 1, wherein the organic contaminant in the organic wastewater is at least one of 4-chlorophenol, bisphenol a, sulfonamide, and rhodamine B.
3. The use according to claim 1, wherein the concentration of organic pollutants in the organic wastewater is 5-20 mg/L, the addition amount of the double metal oxide nano material in each liter of the organic wastewater is 0.05-0.2 g/L, and the addition amount of the PMS is 0.04-0.1 g/L.
4. The use according to claim 1, characterized in that the mass ratio of the nickel salt to the zinc salt is 1:1 to 1:0.7.
5. The use according to claim 1, wherein the nickel salt is Ni (NO 3 ) 2 ·6H 2 O, the zinc salt is Zn (NO 3 ) 2 ·6H 2 O。
6. The use according to claim 1, wherein in step S1, the volume ratio of N, N-dimethylformamide to ethylene glycol is from 7:5 to 9:5; the mass of the terephthalic acid accounts for 55-65% of the mass of the nickel salt.
7. The use according to claim 1, wherein in step S2, the hydrothermal reaction is carried out at a temperature of 140-160 ℃ for a time of 5.5-6.5 h.
8. The use according to claim 1, characterized in that in step S2, after cooling to room temperature, the product obtained is centrifuged and washed three times with N, N-dimethylformamide and absolute ethanol.
9. The use according to claim 1, wherein in step S2, the vacuum drying is performed at a temperature of 60 to 80 ℃ for a time of 8 to 12 hours.
10. The use according to claim 1, wherein in step S3, the heat treatment conditions are: and (3) keeping the precursor at 450-550 ℃ for 20-30 min, and controlling the heating rate to be 2 ℃/min.
11. The use according to claim 1, characterized in that the bi-metal oxide nanomaterial has an egg yolk/shell structure with a 200-300 nm gap between the core and the shell.
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