CN117399007A - A transition metal cluster-single atom composite catalyst and its application - Google Patents
A transition metal cluster-single atom composite catalyst and its application Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- B01J23/74—Iron group metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a transition metal cluster-monoatomic composite catalyst, wherein transition metal is loaded in a cluster and monoatomic modeOn the surface of the carbon layer of the immobilization carrier, the immobilization carrier is prepared by taking zirconium ions as metal centers and organic ligand (HOOC) CH (NH) 2 )‑(X 1 )m‑(X 2 )n‑(X 3 ) And the metal-organic framework formed by assembling p-COOH is prepared by pyrolysis. The composite catalyst disclosed by the invention utilizes the coordination effect of amino groups on ligand branched chains to anchor transition metals, can generate metastable persulfate species with stronger oxidizing ability, can shorten the mass transfer distance between pollutants and active species, and remarkably accelerates the degradation kinetics rate. The invention is based on a non-free radical path to efficiently degrade organic pollutants in water, and can effectively avoid the free radical quenching effect caused by inorganic salt, thereby being particularly suitable for treating salt-containing wastewater.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a transition metal cluster-monoatomic composite catalyst and application thereof in efficiently activating persulfate to degrade toxic organic pollutants in salt-containing wastewater.
Technical Field
In recent years, toxic organic pollutants such as antibiotics, volatile phenols and the like contained in the wastewater cause serious threat to water ecological safety. Fenton oxidation technology is widely applied to organic wastewater treatment, but anions in the saline wastewater can severely consume hydroxyl radicals generated by reaction, so that the operation efficiency of a Fenton method is greatly reduced. Therefore, there is a need to develop novel oxidation techniques to achieve efficient control of toxic organic pollutants in salty organic wastewater.
Compared with the traditional Fenton technology, the heterogeneous advanced oxidation technology based on Persulfate (PS) has the advantages of wide pH application range, recyclable catalyst and the like. The monoatomic catalyst (SAC) reduces the scale of the active site to the atomic level, and the unsaturated coordination structure of the metal and the theoretical 100% atomic utilization rate enable the catalyst to show remarkably improved catalytic activity on activating PS degradation organics. The zirconium-based metal-organic framework can stabilize metal atoms through coordination anchoring and micropore confinement effect, and is an excellent precursor for synthesizing SAC. The Chinese patent publication No. CN113198511B discloses a nitrogen-doped carbon-supported Fe-Co bimetallic single-atom catalyst for efficiently activating persulfate and a preparation method thereof, and uses UIO-66-NH 2 (Zr) is used as a carrier to prepare a catalyst loaded with Fe-Co bimetal single atoms, and the degradation rate of sulfamethoxazole reaches 96.8% in 6min by activating PS; however, N-Dimethylformamide (DMF) organic solvent is used in large amount in the synthesis process and the ligand 2-amino-terephthalamideAcid price is expensive, and is unfavorable for green and economic synthesis of SAC.
In addition, the SAC has single active site and low metal loading, is easily limited by adsorption association, so that the catalytic activity is difficult to further improve, and the supported nanocluster and single-atom coexistence catalyst is widely focused. Wang et al (Applied Catalysis B: environmental,2023, 329, 122569) assembled zinc ions as metal active centers and 2-methylimidazole as organic ligands to form ZIF-8, and controlled the content of Zn/Co by using the ZIF-8 as a carrier to control the center size of the catalyst atoms, wherein cobalt monoatoms are easily aggregated to form cobalt nanoparticles due to high energy in the high-temperature calcination process along with the increase of the cobalt content, and the coexistence state of nanoclusters and monoatoms is difficult to stably maintain. Mo et al (PNAS, 2023, 120, 2300281120) utilize TiO 2 Successful construction of Fe ACs and Fe-N for vectors 4 The removal rate of tetracycline is reduced from 90.81% to 76.53% after 5 cycles of reaction, and the reaction process is affected by the coexisting inorganic anions.
In summary, the carrier has an important influence in the process of preparing the catalyst in which the nanoclusters and the monoatoms coexist, however, the research on the catalyst is limited, and the development of the catalyst in which the nanoclusters and the monoatoms coexist with high efficiency and stability is needed to realize the degradation of toxic organic pollutants in the salt-containing organic wastewater.
Disclosure of Invention
In order to overcome the defects existing in the application and technology of the conventional heterogeneous transition metal catalyst, the invention aims to provide a transition metal cluster-monoatomic composite catalyst and application thereof.
The method uses zirconium ions as metal centers and a metal-organic framework formed by assembling low-price nitrogen-containing organic ligands, adsorbs transition metal ions by utilizing the coordination effect of amino groups on ligand branched chains, and carries out high-temperature calcination to prepare the transition metal cluster-monoatomic composite catalyst.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a transition metal cluster-monoatomic composite catalyst is characterized in that transition metal is loaded on the surface of a carbon layer of an immobilization carrier in a cluster and monoatomic form, wherein the immobilization carrier is prepared from zirconium ions serving as metal centers and an organic ligand (HOOC) CH (NH) 2 )-(X 1 )m-(X 2 )n-(X 3 ) pyrolysis of metal-organic frameworks (Zr-DAAMOF) formed by assembling p-COOH, wherein X 1 、X 2 、X 3 Identical or different, selected from-CH substituted by one or more of H, C1-C6 alkyl, C1-C6 alkoxy, hydroxy, amino, halogen and nitro 2 -, -S-; -S-S-or-O-, m, n, p are the same or different and are selected from 0, 1 or 2.
Preferably, the transition metal is selected from one or more of cobalt, iron, copper, and manganese.
Preferably, the organic ligand is selected from alpha amino acids with two carboxyl functional groups, such as one or more of aspartic acid, glutamic acid and cystine.
The composite catalyst provided by the invention is prepared by the following steps:
s1, taking zirconium ions as metal centers and organic ligands (HOOC) CH (NH) 2 )-(X 1 )m-(X 2 )n-(X 3 ) Stirring a metal-organic framework Zr-DAAMOF formed by assembling p-COOH in a transition metal ion aqueous solution, washing with water, and drying to obtain a transition metal ion-adsorbed Zr-DAA MOF;
s2, calcining the Zr-DAA MOF adsorbed with the transition metal ions in inert gas to obtain the transition metal cluster-monoatomic composite catalyst derived from the Zr-DAA MOF.
Preferably, in step S1, the mass concentration ratio of Zr-DAA MOF to transition metal ion is 1:10-10:1.
preferably, the Zr-DAA MOF in step S1 is obtained by the following method: dissolving aspartic acid and zirconium salt in water, and heating and refluxing at 100-200 ℃ for 1-8h; washing and drying the collected product to obtain Zr-DAA MOF; the molar concentration ratio of the aspartic acid to the zirconium salt is 1:5-5:1; the zirconium salt is zirconium tetrachloride or zirconium oxychloride.
Preferably, the mass concentration of the Zr-DAA MOF in the transition metal ion aqueous solution in the step S1 is 1-5g/L; stirring for 1-12h; the drying temperature is 60-80 ℃ and the drying time is 24-80h.
Preferably, the transition metal ion in the step S1 is one or more of cobalt ion, iron ion, copper ion and manganese ion, and the concentration is 1-30mmol/L.
Preferably, the inert gas in the step S2 is nitrogen or argon; the calcination temperature is 600-900 ℃, the calcination time is 1-8h, and the heating rate is 1-10 ℃/min.
It is another object of the present invention to provide the use of said composite catalyst in a heterogeneous advanced oxidation process.
One specific application of the catalyst is to activate persulfate to degrade toxic organic pollutants in wastewater by using the composite catalyst, wherein the organic pollutants are selected from one or more of tetracycline, rhodamine B, bisphenol A and phenol.
The persulfate is one or more of potassium hydrogen peroxymonosulfate, sodium hydrogen peroxymonosulfate, potassium peroxydisulfate and sodium peroxydisulfate.
Further, the wastewater may further contain an inorganic salt, the anion of which is selected from one or more of chloride ion, sulfate ion, bicarbonate ion and dihydrogen phosphate ion.
Preferably, the inorganic salt ion anion concentration in the water body is 0.1-600mmol/L.
Preferably, the mass ratio of Zr-DAAMOF derived transition metal cluster-monoatomic composite catalyst, persulfate and organic pollutant is 1-5:2-10:1.
Compared with the prior art, the invention has the beneficial effects that:
(1) The Zr-DAAMOF is used as a porous carbon precursor for preparing the transition metal cluster-monoatomic composite catalyst for the first time, the organic ligand does not contain benzene rings or heterocycle, belongs to short-chain aliphatic hydrocarbon ligands, and has smaller aperture with a metal organic framework formed by zirconium. Therefore, the distance of transition metal ions adsorbed into Zr-DAAMOF is shorter than that of metal ions in MOF formed by benzene ring or heterocycle, and metal-metal bonds are easier to be formed close to each other during pyrolysis, so that clusters are generated, and meanwhile, partial metals are distributed in a monoatomic way due to micropore confinement or coordination anchoring, so that a spatially adjacent cluster and monoatomic coexistence structure are formed.
(2) The atomic clusters formed in situ of the catalyst prepared by the invention transfer electrons to single atoms through a carbon carrier, so that the local electron density of the single atom sites is increased, PS adsorbed on the single atom sites is enabled to obtain more electrons, the activation degree is improved, and metastable PS species with stronger oxidizing ability are generated; the catalyst is of a porous structure and large in specific surface area, is favorable for rapid enrichment of various toxic organic pollutants, enables the pollutants and metastable PS to react on the surface of the catalyst, and remarkably accelerates degradation kinetics rate by greatly shortening mass transfer distance between the pollutants and active species.
(3) The Zr-DAA MOF derived transition metal cluster-monoatomic composite catalyst prepared by the invention is suitable for a high-salt environment, free radicals are not generated in the process of efficiently activating persulfate, and the inhibition of catalytic reaction of inorganic salts in the environment through the quenching effect of the free radicals can be fundamentally avoided, so that the PS utilization rate is improved. In addition, the high-concentration inorganic salt ions in the seawater can react with metastable PS to further enrich the types of active species, so that the oxidation of organic matters is enhanced, and the method is suitable for rapidly removing toxic organic pollutants in high-salt water bodies such as the seawater.
Drawings
FIG. 1 is a spherical aberration correcting scanning transmission electron microscope (AC-STEM) image of a transition metal cluster-monoatomic composite catalyst of the invention.
FIG. 2 is a graph showing the effect of various catalysts of the invention on the degradation of tetracycline by persulfate.
FIG. 3 is a graph showing the effect of the transition metal cluster-monoatomic composite catalyst of the invention on activating persulfate to degrade tetracycline in the presence of 600mmol/L of different inorganic salts.
FIG. 4 is a graph showing the effect of the transition metal cluster-monoatomic composite catalyst of the invention on the continuous operation of a column reactor in different water environments for degrading tetracycline.
Detailed Description
The present invention will be specifically described with reference to examples below in order to make the objects and advantages of the present invention more apparent. It should be understood that the following text is intended to describe only one or more specific embodiments of the invention and does not limit the scope of the invention strictly as claimed.
Example 1
A preparation method of a Zr-DAA MOF-derived transition metal cluster-monoatomic composite catalyst comprises the following specific steps:
s1, dispersing 14g of aspartic acid and 11.65g of zirconium tetrachloride in 50mL of ultrapure water respectively, mixing and stirring the two at 25 ℃ for 15-30min until the two are dissolved, then carrying out reflux heating reaction on the obtained mixed solution at 120 ℃ for 4h, centrifugally collecting a white solid product, washing the white solid product with water for three times, and carrying out vacuum drying at 60 ℃ for 24h to obtain the Zr-DAA MOF precursor.
S2, 500mg of the Zr-DAA MOF precursor obtained in the step S1 was dispersed in 90.4mL of ultrapure water, the pH of the solution was adjusted to 5.00-6.00, and then 9.6mL of CoCl having a concentration of 125mmol/L was added 2 ·6H 2 And (3) an O aqueous solution is used for leading the concentration of cobalt ions to be 12mmol/L, stirring is carried out at 25 ℃ for reaction for 4 hours, pink precipitate products are collected by centrifugation, and the Zr-DAA MOF for adsorbing the cobalt ions is obtained after washing with water and vacuum drying at 60 ℃ for 24 hours.
S3, placing the Zr-DAA MOF which is obtained in the step S2 and adsorbs cobalt ions in a crucible, covering a cover, transferring the crucible into a tube furnace, heating to 900 ℃ at a speed of 5 ℃/min under the protection of an inert atmosphere of argon, and calcining for 2 hours. And after the reaction is finished, naturally cooling the tubular furnace to room temperature to prepare the Zr-DAA MOF-derived transition metal cluster-monoatomic composite catalyst.
As can be seen from the spherical aberration correction scanning transmission electron microscope (AC-STEM) image of the Zr-DAA MOF-derived transition metal cluster-monoatomic composite catalyst obtained in step S3 of this example, and FIG. 1, it can be seen that cobalt nanoclusters coexist with monoatoms on the surface of the catalyst, and the catalyst has a porous structure and a large specific surface area (329.64 m 2 /g) cobalt loading was 1.12wt%.
Example 2
Tetracyclines are widely used in the medical and animal industries as a class of broad-spectrum antibiotics, whose residues in environmental bodies of water pose a great threat to human health and ecological environment. This example the Zr-DAA MOF-derived transition metal cluster-monoatomic composite catalyst obtained in example 1 was used to activate potassium hydrogen persulfate composite salts to test their performance on tetracycline degradation under the following specific experimental conditions: 10mg of the catalyst was placed in 100mL of tetracycline solution, wherein the concentration of tetracycline was 20mg/L, the initial pH was 4.55 and the pH was no longer adjusted during the experiment, the temperature of the experiment was 25 ℃. After the catalyst is ultrasonically dispersed for 20min, magnetically stirring for 10min to reach adsorption-desorption equilibrium, and then adding 0.4mL of potassium hydrogen persulfate composite salt solution with the concentration of 20g/L to initiate reaction, wherein the degradation result is shown in a figure 2, and Zr-DAA-C is a catalyst without cobalt; 1 to 16 are the molar concentrations of cobalt ions in step b of example 1; the tetracycline is completely degraded within 10min, and the high efficiency of the catalyst is verified.
Example 3
The procedure is as in example 1, except that the organic ligand used in step S1 is glutamic acid.
The catalyst obtained had a degradation rate of 97.5% for tetracycline within 10min under the same experimental conditions as in example 2.
Example 4
The difference from example 1 is that:
CoCl in step S2 2 ·6H 2 O is changed into FeCl 3 ·6H 2 O. 9.6mL of FeCl with a concentration of 125mmol/L was added 3 ·6H 2 O aqueous solution so that the concentration of iron ions was 12mmol/L.
The catalyst obtained had a degradation rate of 90.1% for tetracycline within 10min under the same experimental conditions as in example 2.
Example 5
The difference is that the persulfate salt used is potassium persulfate as in example 2.
The catalyst obtained had a degradation rate of 94.8% for tetracycline within 10min under the same experimental conditions as in example 2.
Example 6
In order to detect the degradation effect of the catalyst on different toxic organic pollutants, the same example 2 is different in that the organic pollutants are rhodamine B, bisphenol A and phenol respectively, and the degradation rates of the three pollutants are 100.0%, 99.8% and 97.6% respectively within 10min under the same experimental conditions as in example 2, which shows that the catalyst has excellent removal effect on various toxic organic pollutants in water.
Example 7
To examine the effect of the catalyst on the degradation of tetracycline in the presence of a high concentration of inorganic salt, the treatment was the same as in example 2, except that Cl was added to the tetracycline solution, respectively - 、SO 4 2- 、HCO 3 - And H 2 PO 4 - The inorganic salt concentration was 600mmol/L. The results are shown in FIG. 3: the degradation rate of the catalyst to the tetracycline is 100.0%, 94.1%, 100.0% and 96.4% in 10min respectively, which shows that the catalyst can still remove the tetracycline with high efficiency under the coexistence condition of high-concentration inorganic salt; due to the high concentration of Cl-and HCO 3 - The remaining persulfate may be activated to generate active chlorine species, carbonate radicals and hydroxyl radicals, thereby promoting the degradation of the tetracycline.
Example 8
In order to evaluate the application potential of the catalyst in an actual water body, respectively preparing a tetracycline solution with the concentration of 10mg/L by taking ultrapure water, tap water, mountain lake water and Bohai seawater as solvents as a water sample A to be treated; preparing a potassium hydrogen persulfate composite salt solution B with 0.2g/L by taking ultrapure water as a solvent; a column reactor (. Phi.20X 200 mm) was set up with 100mg of catalyst as a packing. The solution A and the solution B enter a column reactor through a peristaltic pump at a flow rate of 0.5mL/min for reaction, and a constant-temperature circulating water tank is used for keeping the temperature of the column reactor at 25 ℃ and the hydraulic retention time at 62.8min; the water body treated by the column catalytic reactor enters the automatic part collector through a peristaltic pump at a flow rate of 1.0 mL/min. The results are shown in FIG. 4: the zero emission time of the tetracycline in the ultrapure water, tap water, mountain lake water and Bohai sea water is respectively as long as 315h, 300h, 312h and 410h. The column reactor has stronger capability for completely degrading the tetracycline in the Bohai sea water, and in the corresponding example 10, the high-concentration chloride ions and bicarbonate ions promote the degradation of the tetracycline, which proves that the catalytic system constructed by the invention has good anti-interference capability and can successfully realize the efficient degradation of toxic organic pollutants in high-salinity water.
Comparative example 1
To demonstrate that cobalt doping in the Zr-DAA MOF-derived transition metal cluster-monoatomic composite catalyst has an increasing effect on the catalytic activity of the catalyst, a catalyst that does not support a transition metal was prepared, which was compared with the catalytic effect difference of the catalyst obtained in example 1. The preparation method is the same as in example 1, except that no cobalt source is added in step S2, the degradation result is shown in FIG. 2, and the degradation rate of the obtained catalyst to tetracycline in 10min is 54.1% under the same experimental conditions as in example 2.
Comparative example 2
The difference from example 1 is that:
the organic ligand used in step S1 is 2,2 '-bipyridine-5, 5' -dicarboxylic acid, and the solvent is N, N-dimethylformamide. 0.16g of 2,2 '-bipyridine-5, 5' -dicarboxylic acid and 0.24mL of triethylamine were dissolved in 40mL of DMF solution, 0.15g of ZrCl 4 And 11mL of acetic acid were dissolved in 40mL of DMF solution, and then the two DMF solutions were mixed and heated at 85℃for 24h. The obtained product is centrifugally washed by DMF and methanol for multiple times by ultrasonic, and is dried in vacuum at 25 ℃ for 24 hours to obtain the zirconium-based metal organic framework precursor.
The catalyst obtained had a degradation rate of 30.1% for tetracycline within 10min under the same experimental conditions as in example 2.
Comparative example 3
The procedure is as in example 1, except that the organic ligand used in step S1 is 5-aminoisophthalic acid.
The catalyst obtained had a tetracycline degradation rate of 42.5% in 10min under the same experimental conditions as in example 2.
While the embodiments of the present invention have been described in detail with reference to the examples, the present invention is not limited to the above embodiments, and it will be apparent to those skilled in the art that various equivalent changes and substitutions can be made therein without departing from the principles of the present invention, and such equivalent changes and substitutions should also be considered to be within the scope of the present invention.
Claims (10)
1. A transition metal cluster-monoatomic composite catalyst is characterized in that transition metal is loaded on the surface of a carbon layer of a fixed carrier in a cluster and monoatomic mode, wherein the fixed carrier is prepared from zirconium ions serving as metal centers and an organic ligand (HOOC) CH (NH) 2 )-(X 1 )m-(X 2 )n-(X 3 ) pyrolysis of metal-organic frameworks formed by p-COOH assembly, wherein X 1 、X 2 、X 3 Identical or different, selected from-CH substituted by one or more of H, C1-C6 alkyl, C1-C6 alkoxy, hydroxy, amino, halogen and nitro 2 -, -S-; -S-S-or-O-, m, n, p are the same or different and are selected from 0, 1 or 2.
2. The composite catalyst according to claim 1, characterized in that the transition metal is selected from one or more of cobalt, iron, copper, manganese.
3. The composite catalyst according to claim 1, characterized in that the organic ligand is selected from the group of alpha amino acids having two carboxyl functions.
4. A composite catalyst according to claim 3, characterized in that the organic ligand is selected from one or more of aspartic acid, glutamic acid, cystine.
5. The composite catalyst according to any one of claims 1 to 4, which is prepared by the following method:
s1, taking zirconium ions as metal centers and organic ligands (HOOC) CH (NH) 2 )-(X 1 )m-(X 2 )n-(X 3 ) Stirring the metal-organic framework formed by assembling the p-COOH in a transition metal ion aqueous solution, washing with water, and drying to obtain the metal-organic framework for adsorbing transition metal ions;
s2, calcining the metal-organic framework material adsorbed with the transition metal ions in inert gas to obtain the transition metal cluster-monoatomic composite catalyst.
6. The composite catalyst according to claim 5, wherein: in the step S1, the mass concentration ratio of the metal-organic framework to the transition metal ions is 1:10-10:1.
7. use of a composite catalyst according to any one of claims 1-6 in a heterogeneous advanced oxidation process.
8. The use according to claim 7, characterized in that the complex catalyst activates persulfates to degrade toxic organic pollutants in wastewater.
9. The use according to claim 7, characterized in that the persulfate is one or more of potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxydisulfate, sodium peroxydisulfate.
10. The use according to claim 7, characterized in that the wastewater contains inorganic salts, the anions of which are selected from one or more of chloride, sulfate, bicarbonate and dihydrogen phosphate.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100209354A1 (en) * | 2007-10-01 | 2010-08-19 | Centre National De La Recherche Scientifique - Cnrs | Organic/inorganic hybrid nanoparticulates made from iron carboxylates |
| US20170326536A1 (en) * | 2016-05-13 | 2017-11-16 | King Fahd University Of Petroleum And Minerals | Metal organic frameworks as catalysts and hydrocarbon oxidation methods thereof |
| CN110449177A (en) * | 2019-08-19 | 2019-11-15 | 中国科学技术大学 | A kind of multifunctional single catalyst atom and preparation method thereof for air comprehensive purification |
| CN112264064A (en) * | 2020-10-09 | 2021-01-26 | 浙江大学 | Preparation method of copper single-atom carbon-based catalyst and application of degrading phenolic organic pollutants |
| CN112337509A (en) * | 2020-11-05 | 2021-02-09 | 北京化工大学 | MOF-based transition metal single-atom catalyst for selective hydrogenation of carbon-carbon triple bonds and preparation method thereof |
| CN112938936A (en) * | 2021-03-17 | 2021-06-11 | 西安交通大学 | Metal atom loaded nano composite material and preparation method thereof |
| CN112973754A (en) * | 2021-03-01 | 2021-06-18 | 南开大学 | Preparation method of novel transition metal monoatomic catalyst loaded on carbon-based material |
| KR20210116321A (en) * | 2020-03-12 | 2021-09-27 | 이화여자대학교 산학협력단 | Pharmaceutical composition including nanozyme and method for preventing or treating proliferative diseases using the same |
| CN114522706A (en) * | 2020-11-04 | 2022-05-24 | 中国科学院大连化学物理研究所 | Carbide-supported noble metal monatomic catalyst, and preparation and application thereof |
| CN116212954A (en) * | 2023-02-20 | 2023-06-06 | 深圳大学 | A MOFs material decorated with high-loaded Pt atoms and its preparation method and application |
-
2023
- 2023-09-28 CN CN202311283546.8A patent/CN117399007B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100209354A1 (en) * | 2007-10-01 | 2010-08-19 | Centre National De La Recherche Scientifique - Cnrs | Organic/inorganic hybrid nanoparticulates made from iron carboxylates |
| US20170326536A1 (en) * | 2016-05-13 | 2017-11-16 | King Fahd University Of Petroleum And Minerals | Metal organic frameworks as catalysts and hydrocarbon oxidation methods thereof |
| CN110449177A (en) * | 2019-08-19 | 2019-11-15 | 中国科学技术大学 | A kind of multifunctional single catalyst atom and preparation method thereof for air comprehensive purification |
| KR20210116321A (en) * | 2020-03-12 | 2021-09-27 | 이화여자대학교 산학협력단 | Pharmaceutical composition including nanozyme and method for preventing or treating proliferative diseases using the same |
| CN112264064A (en) * | 2020-10-09 | 2021-01-26 | 浙江大学 | Preparation method of copper single-atom carbon-based catalyst and application of degrading phenolic organic pollutants |
| CN114522706A (en) * | 2020-11-04 | 2022-05-24 | 中国科学院大连化学物理研究所 | Carbide-supported noble metal monatomic catalyst, and preparation and application thereof |
| CN112337509A (en) * | 2020-11-05 | 2021-02-09 | 北京化工大学 | MOF-based transition metal single-atom catalyst for selective hydrogenation of carbon-carbon triple bonds and preparation method thereof |
| CN112973754A (en) * | 2021-03-01 | 2021-06-18 | 南开大学 | Preparation method of novel transition metal monoatomic catalyst loaded on carbon-based material |
| CN112938936A (en) * | 2021-03-17 | 2021-06-11 | 西安交通大学 | Metal atom loaded nano composite material and preparation method thereof |
| CN116212954A (en) * | 2023-02-20 | 2023-06-06 | 深圳大学 | A MOFs material decorated with high-loaded Pt atoms and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 喻海彬;胡文勇;刘静怡;杨哲;沈良辰;: "钴金属-有机骨架活化过硫酸钠降解废水中的盐酸土霉素", 环境工程学报, no. 09, 31 December 2020 (2020-12-31), pages 234 - 242 * |
| 谢昆等: "纳米技术在水污染控制中的应用", 30 June 2014, 武汉大学出版社, pages: 44 * |
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