CN114160195A - Preparation method and application of water-soluble noble metal cluster catalyst - Google Patents
Preparation method and application of water-soluble noble metal cluster catalyst Download PDFInfo
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Abstract
The invention provides a preparation method of a water-soluble noble metal cluster catalyst, aiming at the defect that cluster particles in the existing noble metal cluster supported catalyst are easy to agglomerate into nano particles with larger particle size, so that the catalytic reaction activity is reducedStably loading noble metal cluster particles in water-soluble monomolecular Cage-NH2The method of the inner part of the cavity is to synthesize water-soluble single molecular Cage-NH2As catalyst carrier, noble metal ion is adsorbed, coordinated and concentrated in Cage-NH2Inside the cage cavity, through NaBH4Reducing to obtain M @ Cage-NH2Catalysts (M: Pd, Pt, Ru, etc.). Due to the single molecular Cage-NH2Good water solubility, so that M @ Cage-NH2The catalyst also has good water solubility, so that the high-efficiency homogeneous catalytic conversion reaction in a water phase system can be realized. More importantly, to M @ Cage-NH2Adding acetone into an aqueous phase homogeneous system of the catalyst, and then adding M @ Cage-NH2The catalyst can be precipitated and collected in a filtering or centrifuging way to realize M @ Cage-NH2The water phase homogeneous phase catalytic reaction and the liquid-solid phase separation recovery of the catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation methods of noble metal cluster supported catalysts, and particularly relates to a method for preparing a water-soluble noble metal cluster catalyst by carrying noble metal clusters in a water-soluble organic cage material limited domain.
Background
Noble metal cluster particles, generally consisting of several to several tens of noble metal atoms, having a particle diameter of less than 2 nm; compared with noble metal nanoparticles (the particle size is more than 2nm), the proportion of the surface metal atoms of the noble metal cluster is higher, so that the noble metal cluster supported catalyst can provide more abundant catalytic active sites in the catalytic reaction, and further has higher catalytic activity. However, the surface energy of the ultrafine noble metal cluster particles is high, so that the noble metal clusters are easily agglomerated into nanoparticles with larger particle size, and the catalytic reaction activity is reduced. Therefore, the construction of a noble metal cluster supported catalyst with high stability and excellent catalytic activity has important industrial catalytic application.
At present, the preparation methods of the noble metal cluster catalyst mainly comprise the following two methods: (1) protecting the surface of the noble metal cluster by using an organic stabilizer so as to prevent the noble metal cluster from agglomerating; for example, the literature reports the use of thiol-containing glutathione molecules to stabilize Au clusters (j.am. chem. soc.2005,127,5261-5270), triphenylphosphine molecules to stabilize Ag clusters (nat. commun.2018,9,744); however, this method requires the use of an excessive amount of organic stabilizer, which covers the surface of the noble metal cluster and makes it difficult to expose its active sites, resulting in a decrease in catalytic activity of the catalyst. (2) The use of a support material having a high specific surface area for anchoring dispersed noble metal clusters; for example: covalent organic framework materials (ACS Central Sci.,2020,6, 869-; however, this method inevitably causes the noble metal clusters to agglomerate into nanoparticles having a large particle size because the interaction force between the metal and the carrier is generally weak.
In addition, in the application aspect of the noble metal cluster or nanoparticle supported catalyst, the catalyst is mainly applied to heterogeneous catalytic reactions such as gas-solid phase and liquid-solid phase; it is known that compared with a heterogeneous catalytic reaction system in which a catalyst can be separated by centrifugation or filtration, the homogeneous catalytic reaction has higher catalytic reaction efficiency because reactants and the catalyst are in the same phase reaction system and are mixed and contacted with each other at a molecular level. Therefore, the soluble noble metal cluster catalyst is designed and constructed, and is applied to catalytic reaction in a homogeneous system, and has important application value.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a noble metal cluster catalyst, which can ensure that noble metal clusters are highly dispersed and stably loaded and can be uniformly dissolved in a water phase system, aiming at the defects of the existing noble metal cluster catalyst preparation technology and the using process.
The invention also aims to realize the high-selectivity catalytic hydrogenation synthesis of important fine organic chemicals such as decahydroquinoline, cyclohexanone, cinnamyl alcohol and the like by utilizing the prepared water-soluble Ru cluster catalyst, Pd cluster catalyst, Pt cluster catalyst and the like.
The technical scheme is as follows for solving the technical problem of the invention:
a preparation method of a water-soluble noble metal cluster catalyst comprises the following specific steps:
the method comprises the following steps: dissolving 1mol of phloroglucinol, 2mol of cyanuric chloride and 1mol of N, N-diisopropylethylamine in 1L of tetrahydrofuran, and stirring at 0 ℃ for reaction for 2 hours; then naturally heating to room temperature, dropwise adding 500mL of acetone solution dissolved with 1mol of phloroglucinol into the solution, and stirring at room temperature for reaction for 72 hours; then adding 500mL of 28 wt% ammonia water into the system, stirring and reacting for 12 hours at room temperature, filtering, washing the white solid with water and acetone for 3 times respectively, and drying for 12 hours at room temperature in a vacuum drying oven to obtain the Cage-NH2A carrier material;
step two: adding Cage-NH2Dissolving the material in deionized water, dripping noble metal salt (ruthenium trichloride, chloropalladate or chloroplatinic acid) solution to coordinate and enrich noble metal ions in Cage-NH2Inside the cage cavity, NaBH is dripped4The solution is used for fully reducing the noble metal ions to be in the elementary substance state and being limited to Cage-NH2The M @ Cage-NH is obtained inside the Cage cavity2A catalyst.
In the first step, the reaction temperature of phloroglucinol, cyanuric chloride and N, N-diisopropylethylamine in tetrahydrofuran is 0 ℃.
In the first step, after 28 wt% of ammonia water is added into the reaction system, the reaction temperature is room temperature, and the stirring speed is 200 and 500 revolutions per minute.
In the step one, the Cage-NH is obtained by adopting a mode of alternately washing and filtering water and acetone and vacuum drying at room temperature2A carrier material.
The step one is Cage-NH2The support material is soluble in water, but in Cage-NH2Adding acetone with the volume ratio of 10-30% to water into the aqueous solution of (1), and adding the mixture of Cage-NH2The support material may be coagulated and collected by filtration or centrifugation.
A single molecular Cage of Cage-NH is arranged in the step I2The cage cavity size of the carrier material is about 0.5-0.6 nm.
The noble metal component in the second step can be Pd, Pt, Ru, etc., and the noble metal loading capacity and Cage-NH2The mass ratio of the carrier is 1-30%.
M @ Cage-NH in the second step2The size of the noble metal cluster in the catalyst is about 0.5-0.6 nm.
M @ Cage-NH in the second step2The catalyst can be uniformly dissolved in an aqueous phase system, and when the molecular weight of the catalyst is equal to M @ Cage-NH2Adding acetone with the volume ratio of 10-30% to water into an aqueous solution system of the catalyst, and then adding M @ Cage-NH2The catalyst can be precipitated and collected in a filtering or centrifuging way to realize the preparation of M @ Cage-NH2The water phase homogeneous phase catalytic reaction and the liquid-solid phase separation recovery of the catalyst.
Ru @ Cage-NH obtained by preparation method of water-soluble precious metal cluster catalyst2The application of the catalyst in catalyzing the hydrogenation of quinoline to synthesize decahydroquinoline specifically comprises the following steps: adding 1g of Ru @ Cage-NH2The catalyst was dissolved in 500mL of water and charged to a 1L autoclave containing 40g of quinoline, with H2Replacing for 3 times, charging 2-3MPa hydrogen, reacting at 90 deg.C under stirring, and detecting conversion rate and selectivity by gas chromatography; pd @ Cage-NH2The application of the catalyst in catalyzing phenol hydrogenation to synthesize cyclohexanone is specifically as follows: adding 1gPd @ Cage-NH2Dissolving a catalyst in 500mL of water, adding the solution into a 1L high-pressure reaction kettle containing 30g of phenol, continuously filling normal-pressure hydrogen under stirring, reacting at the temperature of 60-80 ℃, and tracking and detecting the conversion rate and the selectivity of the reaction by using gas chromatography; pt @ Cage-NH2The application of the catalyst in catalyzing selective catalytic hydrogenation of cinnamyl aldehyde to synthesize cinnamyl alcohol comprises the following specific steps: 1g of Pt @ Cage-NH2The catalyst was dissolved in 500mL of water and charged to a 1L autoclave containing 50g of cinnamaldehyde, washed with H2And (3) replacing for 3 times, filling 1.5MPa of hydrogen, reacting under stirring, and tracking and detecting the conversion rate and the selectivity of the reaction by using gas chromatography. After the reaction is finished, adding 50-150mL of acetone into the reaction system under stirring to dissolve M @ Cage-NH2The catalyst is precipitated and M @ Cage-NH is recovered by filtration or centrifugation2A catalyst.
The preparation method of the water-soluble noble metal cluster catalyst aims at solving the problem that noble metal cluster particles in the prior art are extremely easy to agglomerateProvides a method for stably loading noble metal cluster particles on water-soluble monomolecular Cage-NH for the defect of reducing catalytic reaction activity caused by nanoparticles with larger particle size2An internal method, i.e. firstly synthesizing water-soluble monomolecular Cage-NH2Carrier material, and then noble metal ions are adsorbed, coordinated and enriched in Cage-NH2Inside the cage cavity, through NaBH4Reducing to obtain M @ Cage-NH2Catalysts (M: Pd, Pt, Ru, etc.). Prepared M @ Cage-NH2The catalyst can be dissolved in water in a monomolecular Cage form, and meanwhile, Cage-NH2The molecular Cage has a larger molecular window, which is beneficial to the reaction product molecules and M @ Cage-NH2The noble metal cluster active sites in the catalyst are contacted, thereby realizing high-efficiency catalytic conversion reaction. More importantly, the water-soluble M @ Cage-NH is2The catalyst can be precipitated after acetone is added into a water-soluble system and is collected in a filtering or centrifuging mode to realize the preparation of M @ Cage-NH2The water phase homogeneous phase catalytic reaction and the liquid-solid phase separation recovery of the catalyst.
The invention has the advantages that:
1. water-soluble M @ Cage-NH prepared by the invention2Catalyst, since noble metal clusters are limited to Cage-NH2Inside the cavity of the molecular cage, the noble metal clusters can be effectively prevented from being agglomerated into nanoparticles with larger particle sizes, so that the stability of the noble metal cluster catalyst is improved.
2、M@Cage-NH2The catalyst can be uniformly dissolved in the water phase system, so that the relevant catalytic hydrogenation and other reactions in the water phase system can be efficiently catalyzed in the form of a homogeneous catalyst, and the catalytic reaction performance is improved.
3. Water-soluble M @ Cage-NH2The catalyst can be precipitated after acetone is added into a water phase system, so that the catalyst can be collected in a filtration or centrifugation mode to realize the preparation of M @ Cage-NH2Carrying out water phase homogeneous catalytic reaction and liquid-solid phase separation on the catalyst to recover the catalyst; the catalyst can still maintain stable catalytic activity after being used for 10 times.
Drawings
FIG. 1 shows water-soluble polymers prepared according to examples 1 to 4 of the present inventionSex M @ Cage-NH2A flow chart for preparing the catalyst;
FIG. 2 is a graph of M @ Cage-NH prepared in examples 1-4 of the present invention2Homogeneous dissolution profile in aqueous system and coagulation profile after introduction of acetone;
FIG. 3 shows Ru @ Cage-NH prepared in examples 1-4 of the present invention2、Pd@Cage-NH2、Pt@Cage-NH2Transmission electron micrograph of catalyst.
Detailed Description
Example 1
A preparation method of a water-soluble noble metal cluster catalyst comprises the following specific steps: dissolving 1mol of phloroglucinol, 2mol of cyanuric chloride and 1mol of N, N-diisopropylethylamine in 1L of tetrahydrofuran, and stirring at 0 ℃ for reaction for 2 hours; then naturally heating to room temperature, dropwise adding 500mL of acetone solution dissolved with 1mol of phloroglucinol into the solution, and stirring at room temperature for reaction for 72 hours; then adding 500mL of 28 wt% ammonia water into the system, stirring and reacting for 12 hours at room temperature, filtering, washing the white solid with water and acetone for 3 times respectively, and drying for 12 hours at room temperature in a vacuum drying oven to obtain the Cage-NH2A carrier material.
Example 2
A preparation method of a water-soluble noble metal cluster catalyst comprises the following specific steps: the Cage-NH of example 125g of the material is dissolved in 100mL of deionized water, 30mL of aqueous solution of ruthenium trichloride with the ruthenium metal content of 1g is dripped under the stirring speed of 200-500 r/min, so that the ruthenium ions are coordinated and enriched in Cage-NH2Inside the cage cavity, NaBH is dripped4Solution, ruthenium ions are fully reduced to be in a simple substance state and are limited to Cage-NH2Stirring and reacting for 6 hours in a Cage cavity, and adding 20mL of acetone into the solution system to enable Ru @ Cage-NH2Precipitating, filtering, collecting, and vacuum drying at room temperature overnight to obtain Ru @ Cage-NH2A catalyst.
Example 3
A preparation method of a water-soluble noble metal cluster catalyst comprises the following specific steps: the Cage-NH of example 125g of material was dissolved in 100mL of deionized waterIn the process, 20mL of chloropalladate aqueous solution with 1g of palladium metal content is dripped under the stirring speed of 200-500 r/min to coordinate and enrich palladium ions in Cage-NH2Inside the cage cavity, NaBH is dripped4Solution, so that palladium ions are fully reduced to be in a simple substance state and are limited to Cage-NH2Stirring and reacting for 6 hours in a Cage cavity, and adding 30mL of acetone into the solution system to ensure that Pd @ Cage-NH2Precipitating, filtering, collecting, and vacuum drying at room temperature overnight to obtain Pd @ Cage-NH2A catalyst.
Example 4
A preparation method of a water-soluble noble metal cluster catalyst comprises the following specific steps: the Cage-NH of example 125g of the material is dissolved in 100mL of deionized water, 20mL of chloroplatinic acid aqueous solution with the platinum metal content of 1g is dripped under the stirring speed of 200-500 r/min, so that platinum ions are coordinated and enriched in Cage-NH2Inside the cage cavity, NaBH is dripped4Solution, platinum ions are fully reduced to be in a simple substance state and are limited to Cage-NH2Stirring and reacting for 6 hours in a Cage cavity, and adding 25mL of acetone into the solution system to ensure that Pt @ Cage-NH2Precipitating, filtering, collecting, and vacuum drying at room temperature overnight to obtain Pt @ Cage-NH2A catalyst.
Example 5
Water-soluble Ru @ Cage-NH in example 22The application of the catalyst in catalyzing the hydrogenation of quinoline to synthesize decahydroquinoline specifically comprises the following steps: adding 1g of Ru @ Cage-NH2The catalyst was dissolved in 500mL of water and charged to a 1L autoclave containing 40g of quinoline, with H2Replacing for 3 times, charging 2-3MPa hydrogen, reacting at 90 deg.C under stirring, and detecting conversion rate and selectivity by gas chromatography; after 12h of reaction, the conversion rate of the reactant quinoline is 100%, and the selectivity of the product decahydroquinoline is 99%. After the reaction is finished, adding 100mL of acetone into the reaction system under stirring to dissolve Ru @ Cage-NH2The catalyst is precipitated and Ru @ Cage-NH is recovered by filtration2A catalyst. Ru @ Cage-NH2After the catalyst is reused for 10 times, the conversion rate of quinoline is still higher than 98 percent, and the product is producedThe selectivity of the substance decahydroquinoline is higher than 99%. Shows that the Ru cluster supported water-soluble catalyst Ru @ Cage-NH provided by the invention2Has excellent catalytic performance and catalytic stability.
Example 6
Water-soluble Pd @ Cage-NH in example 32The application of the catalyst in catalyzing phenol hydrogenation to synthesize cyclohexanone is specifically as follows: 1g of Pd @ Cage-NH2Dissolving a catalyst in 500mL of water, adding the solution into a 1L high-pressure reaction kettle containing 30g of phenol, continuously filling normal-pressure hydrogen under stirring, reacting at the temperature of 60-80 ℃, and tracking and detecting the conversion rate and the selectivity of the reaction by using gas chromatography; after 10 hours of reaction, the conversion rate of the reactant phenol is 100 percent, and the selectivity of the product cyclohexanone is 98 percent. After the reaction, 100mL of acetone was added to the reaction system with stirring to dissolve Pd @ Cage-NH2The catalyst is precipitated and Pd @ Cage-NH is recovered by a filtration mode2A catalyst. Pd @ Cage-NH2After the catalyst is reused for 10 times, the conversion rate of phenol is still higher than 96%, and the selectivity of the product cyclohexanone is higher than 98%. Shows that the Pd cluster supported water-soluble catalyst Pd @ Cage-NH provided by the invention2Has excellent catalytic activity and catalytic stability.
Example 7
Water soluble Pt @ Cage-NH in example 42The application of the catalyst in catalyzing selective catalytic hydrogenation of cinnamyl aldehyde to synthesize cinnamyl alcohol comprises the following specific steps: 1g of Pt @ Cage-NH2The catalyst was dissolved in 500mL of water and charged to a 1L autoclave containing 50g of cinnamaldehyde, washed with H2Replacing for 3 times, charging 1.5MPa hydrogen, reacting under stirring, and detecting the conversion rate and selectivity of the reaction by gas chromatography tracking; after the reaction is carried out for 15 hours, the conversion rate of the reactant cinnamaldehyde is 98%, and the selectivity of the product cinnamyl alcohol is 96%. After the reaction, 80mL of acetone was added to the reaction system with stirring to dissolve Pt @ Cage-NH2The catalyst is precipitated and Pt @ Cage-NH is recovered by a filtering mode2A catalyst. Pt @ Cage-NH2The catalyst is reused for 10 times, the conversion rate of the cinnamyl aldehyde is still higher than 96%, and the selectivity of the product cinnamyl alcohol is higher than 96%. Shows that the Pt cluster supported type provided by the inventionWater-soluble catalyst Pt @ Cage-NH2Has excellent catalytic activity and catalytic stability.
Claims (9)
1. A preparation method of a water-soluble noble metal cluster catalyst is characterized by comprising the following steps:
the method comprises the following steps: the method is characterized in that phloroglucinol, cyanuric chloride and ammonia water are used as raw materials, and a water-soluble monomolecular Cage-NH with abundant N, O atoms and amino groups in a synthetic structure2A carrier material;
step two: adding Cage-NH2Dissolving the material in deionized water, dripping noble metal salt solution to coordinate and enrich noble metal ions in Cage-NH2Inside the cage cavity, NaBH is dripped4The solution is used for fully reducing the noble metal ions to be in the elementary substance state and being limited to Cage-NH2The M @ Cage-NH is obtained inside the Cage cavity2Catalysts (M represents Pd, Pt, Ru, etc.);
step three: m @ Cage-NH2The catalyst is dissolved in the water phase, and the volume ratio of acetone to water is 10-30% to make M @ Cage-NH2The catalyst is precipitated from the water solution, filtered and dried in vacuum at room temperature to obtain powdery M @ Cage-NH2A catalyst.
2. The method for preparing a water-soluble noble metal cluster catalyst according to claim 1, wherein: the catalyst carrier is a monomolecular Cage-NH2(ii) a Step one single molecular Cage-NH2The preparation method comprises the steps of firstly dissolving 1mol of phloroglucinol, 2mol of cyanuric chloride and 1mol of N, N-diisopropylethylamine in 1L of tetrahydrofuran, and stirring for reaction for 2 hours at the temperature of 0 ℃; then naturally heating to room temperature, dropwise adding 500mL of acetone solution dissolved with 1mol of phloroglucinol into the solution, and stirring at room temperature for reaction for 72 hours; then adding 500mL of 28 wt% ammonia water into the system, stirring and reacting for 12 hours at room temperature, filtering, washing the white solid with water and acetone for 3 times respectively, and drying for 12 hours at room temperature in a vacuum drying oven to obtain the Cage-NH2A carrier material.
3. The method for producing a water-soluble noble metal cluster catalyst according to claims 1 and 2, characterized in that: Cage-NH2The support material is soluble in water, but in Cage-NH2Adding acetone with the volume ratio of 10-30% to water into the aqueous solution of (1), and adding the mixture of Cage-NH2The support material may be coagulated and collected by filtration or centrifugation.
4. The method for producing a water-soluble noble metal cluster catalyst according to claims 1 and 2, characterized in that: single molecule Cage-NH2The cage cavity size of the carrier material is about 0.5-0.6 nm.
5. The method for preparing a water-soluble noble metal cluster catalyst according to claim 1, wherein: in the second step, M @ Cage-NH2The noble metal M component in the catalyst can be Pd, Pt, Ru, etc., and the loading amount of the noble metal and the Cage-NH2The mass ratio of the carrier is 1-30%, and the size of the noble metal cluster is about 0.5-0.6 nm.
6. The method for preparing a water-soluble noble metal cluster catalyst according to claim 1, wherein: m @ Cage-NH prepared in the second step and the third step2The catalyst can be uniformly dissolved in an aqueous phase system and can react when the molecular weight of the catalyst is equal to M @ Cage-NH2Adding acetone with the volume ratio of 10-30% to water into a water-soluble system of the catalyst, and then adding M @ Cage-NH2The catalyst may be coagulated and collected by filtration or centrifugation.
7. The method for producing a water-soluble noble metal cluster catalyst according to claims 1 and 6, characterized in that: prepared Ru @ Cage-NH2The cluster supported catalyst catalyzes a quinoline compound to be hydrogenated to synthesize a decahydroquinoline compound in a water phase homogeneous system under the hydrogen atmosphere of 2-3MPa, and the reaction conversion rate and the selectivity are both higher than 99%.
8. The method for producing a water-soluble noble metal cluster catalyst according to claims 1 and 6, characterized in that: prepared Pd @ Cage-NH2The cluster supported catalyst catalyzes phenol to synthesize cyclohexanone by hydrogenation in an aqueous phase homogeneous system under the condition of normal pressure and hydrogen atmosphere and at the temperature of 60-80 ℃, the reaction conversion rate is up to 100 percent, and the selectivity of the cyclohexanone is higher than 98 percent.
9. The method for producing a water-soluble noble metal cluster catalyst according to claims 1 and 6, characterized in that: prepared Pt @ Cage-NH2The cluster supported catalyst catalyzes the selective hydrogenation of the cinnamyl aldehyde to synthesize the cinnamyl alcohol in a water-phase homogeneous system under the hydrogen atmosphere of 1.5MPa, the reaction conversion rate is up to 98 percent, and the cinnamyl alcohol selectivity is higher than 96 percent.
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| CN119746648A (en) * | 2024-12-30 | 2025-04-04 | 北京工业大学 | A chlorine-resistant and acid-resistant composite nanofiltration membrane and its preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19710376A1 (en) * | 1997-03-13 | 1998-09-17 | Clariant Gmbh | Catalyst for the hydrogenation dehalogenation of alpha-halogenated carboxylic acids and a process for its preparation |
| US20050261125A1 (en) * | 2004-05-24 | 2005-11-24 | Tanaka Kikinzoku Kogyo K.K. | Catalyst and process for preparing the same |
| US20080033146A1 (en) * | 2006-08-01 | 2008-02-07 | Headwaters Nanokinetix, Inc. | Methods for manufacturing aryl-aryl coupled polymers |
| US20080268159A1 (en) * | 2005-09-29 | 2008-10-30 | Hirohito Hirata | Production Method of Precious Metal Catalyst |
| WO2020252536A1 (en) * | 2019-06-19 | 2020-12-24 | The University Of Adelaide | Hydrogen-bonded organic framework systems |
| CN112280053A (en) * | 2020-09-30 | 2021-01-29 | 中南大学 | Two-dimensional COFs nanosheet based on cage-shaped molecular building block and application thereof |
-
2021
- 2021-12-24 CN CN202111602755.5A patent/CN114160195A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19710376A1 (en) * | 1997-03-13 | 1998-09-17 | Clariant Gmbh | Catalyst for the hydrogenation dehalogenation of alpha-halogenated carboxylic acids and a process for its preparation |
| US20050261125A1 (en) * | 2004-05-24 | 2005-11-24 | Tanaka Kikinzoku Kogyo K.K. | Catalyst and process for preparing the same |
| US20080268159A1 (en) * | 2005-09-29 | 2008-10-30 | Hirohito Hirata | Production Method of Precious Metal Catalyst |
| US20080033146A1 (en) * | 2006-08-01 | 2008-02-07 | Headwaters Nanokinetix, Inc. | Methods for manufacturing aryl-aryl coupled polymers |
| WO2020252536A1 (en) * | 2019-06-19 | 2020-12-24 | The University Of Adelaide | Hydrogen-bonded organic framework systems |
| CN112280053A (en) * | 2020-09-30 | 2021-01-29 | 中南大学 | Two-dimensional COFs nanosheet based on cage-shaped molecular building block and application thereof |
Non-Patent Citations (3)
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119746648A (en) * | 2024-12-30 | 2025-04-04 | 北京工业大学 | A chlorine-resistant and acid-resistant composite nanofiltration membrane and its preparation method |
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