CN115722229A - Bimetal oxide nano material and preparation method and application thereof - Google Patents
Bimetal oxide nano material and preparation method and application thereof Download PDFInfo
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Images
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
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 continuing stirring until the mixture is fully and uniformly mixed; s2, transferring the solution obtained in the step S1 into a polytetrafluoroethylene reaction kettle inner container, sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve into an oven, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying in vacuum to obtain a precursor; and S3, carrying out 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 treatment of various organic wastewater and remediation of 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 bimetal oxide nano material with a yolk/shell structure as well as a preparation method and application thereof.
Background
Advanced oxidation technology based on Peroxymonosulfate (PMS) may 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 a catalyst and PMS oxidant 4 ·- ) Hydroxy group (a) · OH), singlet oxygen: ( 1 O 2 ) And the active species realize the high-efficiency oxidative decomposition of the toxic refractory pollutants in the water. However, various inorganic ions, humus and other soluble organic matters in water are easy to react with free radicals, so that the ineffective consumption of the free radicals is caused, the removal efficiency of target pollutants by the traditional process is obviously reduced, and the treatment cost is increased. Compared with the prior art, the advanced oxidation process based on the adsorption free radicals has higher oxidant utilization efficiency due to the fact that the adsorbable pollutants react on the surface of the catalyst, and has obvious advantages in practical water treatment application.
The selection and design of the catalyst are particularly critical to the PMS advanced oxidation technology. The transition metal oxide has the advantages of low cost, environmental friendliness, flexible and adjustable properties and the like, is widely used as a Fenton-like catalyst, and is mainly concentrated on a catalytic reaction system of free radicals. Catalysts that have been reported to achieve adsorbed-state free radical oxidation pathways include iron oxides, cobalt sulfides, and the like. There have been few studies to find that the bimetallic oxides exhibit superior catalytic activity to the monometallic oxide catalysts. For example, a NiO-ZnO heterojunction composite catalyst is used for activating PMS, meanwhile, pollutants are degraded through pathways such as free radicals and adsorbed radicals, and the catalytic activity of the catalyst is remarkably superior to that of single NiO and ZnO. However, the preparation process of the NiO-ZnO heterojunction catalyst is complicated, and usually, znO with a hollow sphere structure is synthesized first, and then a NiO-ZnO composite material is generated through a secondary hydrothermal reaction, or a NiO-modified ZnO micro-flower structure composite material is generated by re-dispersing flower-shaped ZnO particles into a nickel nitrate solution. In addition, the existing NiO-ZnO heterojunction catalyst generally has the problems of low activity, metal ion dissolution and the like (Ni in the reaction process) 2+ And Zn 2+ The dissolution amount is respectively as high as 0.3mg/L and 13 mg/L), thereby greatly reducing the stability of the cyclic use of the catalyst.
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 existing NiO-ZnO two-step synthesis method, the invention provides a novel preparation method of a bimetallic oxide nano material with an egg yolk/shell structure, optimizes the structure and the performance of the bimetallic oxide nano material, and the nano material can be used as a catalyst for treating various organic wastewater and repairing polluted water environment. According to the invention, the NiO-ZnO composite material with the yolk/shell structure is obtained by a one-step hydrothermal method, the mesoporous shell of the nano reactor with the yolk/shell structure is beneficial to rapid diffusion of reactant molecules, the concentration of reactants and free radicals can be improved by an internal cavity through a confinement effect, and power is hopefully provided 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 bimetal 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 continuing stirring until the mixture is fully and uniformly mixed;
s2, transferring the solution obtained in the step S1 into a polytetrafluoroethylene reaction kettle inner container, sleeving a stainless steel kettle sleeve, placing the stainless steel kettle sleeve into an oven, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying in vacuum to obtain a precursor;
and S3, carrying out 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.
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 the S1 step, the volume ratio of N, N-Dimethylformamide (DMF) to ethylene glycol is 7 to 9; the mass of the terephthalic acid accounts for 55 to 65 percent of that 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 the S2 step, after cooling to room temperature, the resulting product is centrifuged and washed three times each 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 the step S3, the heat treatment conditions are: the precursor is kept at 450-550 ℃ for 20-30 min, and the heating rate is controlled to be 2 ℃/min.
The invention also relates to a bimetallic oxide nano material which is prepared by the preparation method and has a yolk/shell structure, and a gap of 200-300 nm exists between a core and a shell.
The invention also relates to application of the bimetallic oxide nano material in degradation of organic pollutants in organic wastewater by activating PMS. Further preferably, the organic pollutant in the organic wastewater can be at least one of 4-chlorophenol (4-CP), bisphenol A (BPA), sulfanilamide (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 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:
(1) The method adopts a one-step hydrothermal method to directly synthesize the yolk/shell structure NiO-ZnO bimetallic oxide nano material, greatly simplifies the synthesis process, dissolves metal salt in the mixed solution of N, N-dimethylformamide and glycol, and forms the yolk/shell structure NiO-ZnO oxide after centrifugal calcination without any template.
(2) The NiO-ZnO bimetal oxide nano material prepared by the invention has a unique yolk/shell structure, and the catalytic degradation efficiency of the yolk/shell structure is obviously enhanced. The porous shell layer can protect the wrapped catalyst from being interfered by bad environment in solution, and the limited cavity environment generates instant high concentrationDegree of SO 4 · -、 · OH provides a driving force for promoting the catalytic oxidation of organic pollutants such as 4-CP and the like, and the suggestion is also that the multifunctional NiO-ZnO yolk/shell nano reactor can bring great expandability so as to enhance the catalytic degradation of the pollutants in various environments.
(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 Ni in a 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 with reference to the following figures and examples:
FIG. 1: SEM image and TEM image of the yolk/shell NiO-ZnO nano material of example 1;
FIG. 2: the XRD pattern of the yolk/shell NiO-ZnO nanomaterial of example 1;
FIG. 3: the yolk/shell NiO-ZnO nanomaterial of example 1 activates the degradation performance of PMS to 4-CP;
FIG. 4: the change of the degradation performance of the yolk/shell NiO-ZnO nano material to 4-CP is carried out after the yolk/shell NiO-ZnO nano material is recycled for 4 times;
FIG. 5 is a schematic view of: the yolk/shell NiO-ZnO nanomaterial of example 1 can activate PMS to degrade various pollutants;
FIG. 6: the yolk/shell NiO-ZnO nano material of example 1 activates PMS to degrade 4-CP in different water environments;
FIG. 7: the yolk/shell NiO-ZnO nanomaterial of example 1 activates the concentration of ion elution in the PMS system.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It is to be understood that these descriptions are only illustrative and are not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
EXAMPLE 1 preparation of NiO-ZnO bimetallic oxide nanomaterials
1. 0.25g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in a mixed solution of 40mL of N, N-dimethylformamide and 25mL of ethylene glycol, and 0.25g of Zn (NO) was added after the O was completely dissolved 3 ) 2 ·6H 2 O, stirring for half an hour at room temperature, adding 0.15g of terephthalic acid, and continuing stirring for 1 hour until the materials are fully and uniformly mixed.
2. Transferring the bright green solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle inner container with the volume of 100mL, sleeving a stainless steel kettle sleeve, putting the stainless steel kettle sleeve into an oven, heating the stainless steel kettle sleeve to 150 ℃ in a program manner, carrying out hydrothermal reaction for 6 hours, naturally cooling, cooling and taking out; and centrifuging the obtained green precipitate, washing the precipitate by using DMF (dimethyl formamide) and absolute ethyl alcohol for three times respectively, and performing vacuum drying at the temperature of 60 ℃ for 12 hours to obtain a 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 same preparation conditions as in example 1 were followed, except that Zn (NO) was not added in step (1) 3 ) 2 ·6H 2 O, addition of Ni (NO) only 3 ) 2 ·6H 2 O。
Comparative example 2 preparation of ZnO Material
The same preparation conditions as in example 1 were followed, except that Ni (NO) was not added in step (1) 3 ) 2 ·6H 2 O, addition of Zn (NO) only 3 ) 2 ·6H 2 O。
The NiO-ZnO bimetal oxide nano material synthesized in the example 1 is characterized and analyzed:
and (3) characterizing the morphology and the structure of the material, namely, uniformly grinding the material and then performing Scanning Electron Microscope (SEM) and X-ray diffraction (XRD) characterization. As shown in FIG. 1, the SEM image showed that the NiO-ZnO had an egg yolk shell microsphere morphology of 2-3 μm in diameter, and hard egg yolk microspheres and thin shells were clearly observed in the broken NiO-ZnO microspheres; the TEM image shows that there is a 200-300 nm gap between the shell and the core, indicating the formation of a cavity structure; as shown in FIG. 2, the XRD diffraction spectrum of the NiO-ZnO bimetal oxide nano material proves the existence of two phases of NiO and ZnO.
Example 2 application to the removal of 4-CP from Water
2mg of NiO-ZnO nanoparticles are dissolved in 20mL of 10mg/L4-CP solution, the solution is subjected to ultrasonic treatment at room temperature for 5min, then the solution is continuously stirred for 10min to enable NiO-ZnO to reach adsorption balance, 40 muL of 25g/L PMS stock solution is added to initiate reaction, and the corresponding degradation rate curve of 4-CP in the NiO-ZnO/PMS system is shown in figure 3. The PMS system in FIG. 3 represents the removal efficiency of 4-CP when PMS exists alone, the NiO-ZnO system represents the removal efficiency of 4-CP when NiO-ZnO exists alone, the NiO/PMS system and the ZnO/PMS system respectively represent the removal effect of 4-CP when NiO, znO and PMS coexist, and the NiO + ZnO/PMS system represents the removal effect of 4-CP when NiO, znO and PMS coexist. As shown in FIG. 3, only 4% of the 4-CP was degraded when the blank PMS or NiO-ZnO was added alone, indicating that the intrinsic oxidizing ability of PMS and the adsorbing ability 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 blank NiO/PMS and ZnO/PMS systems, and the synergistic effect between Ni and Zn elements and the driving force for activating PMS are revealed. Meanwhile, detecting Ni in the NiO-ZnO/PMS system after reaction 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).
Analysis of catalytic reaction pathway: ethanol and tert-butyl alcohol are selected as radical trapping agents and added into a NiO-ZnO/PMS reaction system, and the situation that the degradation of 4-CP cannot be inhibited is found, and the existence of radicals in a bulk solution is eliminated. Phenol was chosen as the quencher for surface bound radicals, degradation performance was almost 100% inhibited. In the process of SO 4 · -、 · In probe experiments with OH, the presence of surface bound radicals can be fully demonstrated by detecting the degradation of benzoic acid and methylene blue probe contaminants. Meanwhile, when an electron paramagnetic resonance spectrum (EPR) test is carried out, sodium fluoride is added to promote the release of surface bound free radicals, signals of the free radicals are captured in the solution, and the mechanism of degrading 4-CP by the system is verified again to be that the surface bound free radicals。
Example 3 Cyclic stability of yolk/shell NiO-ZnO bimetallic oxide nanomaterials
The NiO-ZnO bimetallic oxide nanomaterial in example 1 is used as a catalyst material for pollutant degradation, the specific treatment method for removing 4-CP in water is the same as that in example 2, the catalyst is collected by centrifugation after each experimental reaction, the steps are repeated after the catalyst is washed by deionized water, and the cycle test is carried out for four times, wherein the reaction time of each cycle is 20 minutes. As shown in FIG. 4, the 4-CP efficiency of the yolk/shell NiO-ZnO nanomaterial degradation was still as high as 95% in the first four cycles. After drying the material collected after the fourth cycle, the material was calcined to remove the residues of surface contaminant intermediates, and the above experiment was repeated to confirm the recovery of the catalytic performance of the catalyst. Therefore, the catalyst shows excellent cycle stability in the aspect of activating PMS to degrade organic pollutants.
Example 4 yolk/shell NiO-ZnO/PMS System for treatment of actual Water samples and various contaminants
The yolk/shell NiO-ZnO/PMS bimetal oxide nano material obtained in the example 1 is added into a solution taking different pollutants as treatment objects, wherein the concentrations of the catalyst, PMS, 4-CP and other pollutants are kept consistent with those in the example 2. FIG. 5 is a graph of the degradation rates of different contaminants in the NiO-ZnO/PMS system. Tests prove that the NiO-ZnO/PMS system constructed by the invention can completely remove different organic pollutants (such as 4-CP, BPA, SA and RhB) within 20 minutes.
Deionized water, tap water and lake water are respectively selected to simulate the actual water environment, specifically, a lake water sample (the total organic carbon concentration is 33 mg/L), a tap water sample (the total organic carbon concentration is 20 mg/L) and deionized water are respectively taken, wherein the concentrations of the catalyst, the PMS and the 4-CP are all consistent with those in the example 2. FIG. 6 is a 4-CP degradation rate curve when different water samples are used as reaction media, wherein the Deionind water represents a deionized water sample, the Tap water represents a Tap water sample, and the Lake water represents a Lake water sample, and as can be seen from FIG. 6, the NiO-ZnO/PMS system can realize complete degradation of 4-CP within 25min under different water quality conditions, which proves that the system has good environmental applicability and water treatment application prospect.
The yolk/shell NiO-ZnO bimetallic nano material prepared by the method has excellent catalytic performance, and is mainly attributed to the synergistic effect of Ni and Zn elements and the double synergistic effect of yolk and shell. (1) The activation effect of the NiO-ZnO bimetal 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 bimetal oxide (figure 3). (2) The design of the yolk/shell structure shows the potential of the NiO-ZnO nano reactor in environmental remediation. The NiO-ZnO heterojunction catalyst of egg yolk/shell structure achieved 100% degradation of 10mg/L bisphenol A in 10 minutes (FIG. 5). The porous shell layer allows small-molecule reactants to freely enter, protects the wrapped catalyst from interference of severe components of chloride ions and nitrate ions in the solution, and even if the active sites of the outer shell layer are occupied, the catalytic sites of the inner cavity still remain active. Advantageously, the cavity between the yolk and the shell provides a microenvironment for reaction such that a high concentration of SO is instantaneously present 4 ·- 、 · OH and 4-CP are limited in a limited space, and the confinement effect provides a driving force for promoting the catalytic oxidation of the 4-CP.
It should be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundary of the appended claims, or the equivalents of such scope and boundary.
Claims (10)
1. The preparation method of the bimetallic oxide nano material is characterized by comprising the following steps of:
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 continuing stirring until the mixture is fully and uniformly mixed;
s2, transferring the solution obtained in the step S1 into a polytetrafluoroethylene reaction kettle inner container, sleeving a stainless steel kettle sleeve on the polytetrafluoroethylene reaction kettle inner container, placing the stainless steel kettle sleeve in an oven, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, washing, and drying in vacuum to obtain a precursor;
and S3, carrying out heat treatment on the precursor to obtain the NiO-ZnO nano material.
2. The production method according to claim 1, wherein the mass ratio of the nickel salt to the zinc salt is 1.
3. The method 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。
4. The production method according to claim 1, wherein in the S1 step, the volume ratio of N, N-dimethylformamide to ethylene glycol is 7 to 9; the mass of the terephthalic acid accounts for 55 to 65 percent of the mass of the nickel salt.
5. The method according to claim 1, wherein the hydrothermal reaction is carried out at 140 to 160 ℃ for 5.5 to 6.5 hours in the step S2.
6. The method according to claim 1, wherein, in the step S2, after cooling to room temperature, the resulting product is centrifuged and washed three times with N, N-dimethylformamide and absolute ethanol.
7. The method according to claim 1, wherein the vacuum drying is performed at 60 to 80 ℃ for 8 to 12 hours in the step S2.
8. The method according to claim 1, wherein in the step S3, the heat treatment conditions are: the precursor is kept at 450-550 ℃ for 20-30 min, and the heating rate is controlled to be 2 ℃/min.
9. A bimetal oxide nano material, which is prepared by the preparation method of any one of claims 1 to 8, has a yolk/shell structure, and a gap of 200 to 300nm exists between a core and a shell.
10. Use of the bimetallic oxide nanomaterial according to claim 9 in activating PMS to degrade organic pollutants in organic waste water.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITPD20080188A1 (en) * | 2008-06-26 | 2009-12-27 | Univ Padova | "HAZELNUT-SHELL" ELECTROCATALIZERS BASED ON MONO / MULTI-METAL CARBONITRURES FOR LOW TEMPERATURE FUEL CELLS (PEMFC, DMFC, AFC AND PAFC) AND ELECTROLYZERS |
| KR20170141459A (en) * | 2016-06-15 | 2017-12-26 | 한국과학기술원 | Reduction method of carbon dioxide using zinc based catalyst particle having core-shell structure and apparatus therefor |
| CN108585062A (en) * | 2018-04-02 | 2018-09-28 | 厦门大学 | A kind of more shell yolk-eggshell nano-hollow balls of bimetallic without method for preparing template |
| CN109019705A (en) * | 2018-08-01 | 2018-12-18 | 济南大学 | A kind of MOF induces the preparation method of three-dimensional shell sheath structure zinc oxide combined oxidation nickel gas sensitive |
| DE102018129499A1 (en) * | 2017-11-27 | 2019-05-29 | Uniwersytet Jagielloński | Composite material in the form of solid particles with core-shell active phase structure, process for obtaining such composite material and its use |
| CN112038632A (en) * | 2020-09-18 | 2020-12-04 | 中国人民解放军军事科学院防化研究院 | Carbon-oxazine composite water-based negative electrode material and application thereof |
| CN114713263A (en) * | 2022-04-18 | 2022-07-08 | 中国科学技术大学 | Load monatomic material with core-shell structure, and preparation method and application thereof |
-
2022
- 2022-11-04 CN CN202211376274.1A patent/CN115722229B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITPD20080188A1 (en) * | 2008-06-26 | 2009-12-27 | Univ Padova | "HAZELNUT-SHELL" ELECTROCATALIZERS BASED ON MONO / MULTI-METAL CARBONITRURES FOR LOW TEMPERATURE FUEL CELLS (PEMFC, DMFC, AFC AND PAFC) AND ELECTROLYZERS |
| KR20170141459A (en) * | 2016-06-15 | 2017-12-26 | 한국과학기술원 | Reduction method of carbon dioxide using zinc based catalyst particle having core-shell structure and apparatus therefor |
| DE102018129499A1 (en) * | 2017-11-27 | 2019-05-29 | Uniwersytet Jagielloński | Composite material in the form of solid particles with core-shell active phase structure, process for obtaining such composite material and its use |
| CN108585062A (en) * | 2018-04-02 | 2018-09-28 | 厦门大学 | A kind of more shell yolk-eggshell nano-hollow balls of bimetallic without method for preparing template |
| CN109019705A (en) * | 2018-08-01 | 2018-12-18 | 济南大学 | A kind of MOF induces the preparation method of three-dimensional shell sheath structure zinc oxide combined oxidation nickel gas sensitive |
| CN112038632A (en) * | 2020-09-18 | 2020-12-04 | 中国人民解放军军事科学院防化研究院 | Carbon-oxazine composite water-based negative electrode material and application thereof |
| CN114713263A (en) * | 2022-04-18 | 2022-07-08 | 中国科学技术大学 | Load monatomic material with core-shell structure, and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| GUO-CHANG LI等: "MOF-derived hierarchical double-shelled NiO/ZnO hollow spheres for high-performance supercapacitors", 《DALTON TRANSACTIONS》, pages 13311 - 13316 * |
| JIANG, H等: "Enhanced activation of peroxymonosulfate with metal-substituted hollow MxCo3-xS4 polyhedrons for superfast degradation of sulfamethazine", 《CHEMICAL ENGINEERING JOURNAL》, pages 123302 * |
| 柳后起等: "环太湖水体污染现状分析", 《生态环境学报》, pages 2262 - 2269 * |
| 蔡秋兰: "ZIF-8衍生Co、Ni单原子催化剂的制备及其催化性能", 《中国优秀硕士学位论文全文数据库》, pages 016 - 775 * |
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