CN104525264A - Amino metal organic framework material containing active metal component as well as preparation method and application of amino metal organic framework material - Google Patents
Amino metal organic framework material containing active metal component as well as preparation method and application of amino metal organic framework material Download PDFInfo
- Publication number
- CN104525264A CN104525264A CN201410781464.0A CN201410781464A CN104525264A CN 104525264 A CN104525264 A CN 104525264A CN 201410781464 A CN201410781464 A CN 201410781464A CN 104525264 A CN104525264 A CN 104525264A
- Authority
- CN
- China
- Prior art keywords
- active metal
- metal component
- organic framework
- framework material
- ammonobase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides an amino metal organic framework material containing an active metal component. The amino metal organic framework material is used as a carrier; and the active metal component is dispersed in the carrier, wherein the weight of the active metal component is 0.05-15% of that of the amino MOFs material. According to the invention, a mixed solution is formed from the carrier and an active metal precursor containing a carbanyl group; amino in the MOFs material is reacted with the carbanyl group in the active metal precursor, so that the active metal precursor is connected to the MOFs material; then, the material is prepared through a reduction method; uniform dispersion of the active metal component in the MOFs material is realized; when the material is used as the catalyst, the catalytic effect is obvious because of high dispersion of the active component, for example, the amino metal organic framework material is used in a process for preparing aromatic amine by hydrogenation reduction of an aromatic nitro compound, etc.
Description
Technical field
The present invention relates to the material be made up of carrier and active metal component, be specifically related to a kind of comprise active metal component ammonobase organic framework material, its preparation method and application.
Background technology
Aromatic nitro compound is a kind of common pollutant in industrial wastewater.Aromatic amine is then a kind of important chemical intermediate, is widely used in the industries such as pharmacy, plastics, printing and dyeing and Cosmetic Manufacture.Therefore, people manage to utilize aromatic nitro compound to prepare aromatic amine, mainly contain iron powder reducing method, electrolytic reduction and catalytic hydrogenation method at present.The wherein catalytic hydrogenation process underproduction, pollute little, therefore enjoy people parent to look at.
The catalytic hydrogenating reduction aromatic nitro compound key prepared in aromatic amine technique is hydrogenation catalyst, and efficient hydrogenation catalyst is conducive to improving the conversion ratio of aromatic nitro compound and the selective of aromatic amine.The hydrogenation catalyst of current bibliographical information is mainly divided into non-precious metal catalyst and noble metal catalyst.Non-precious metal catalyst is as low in Ni, Co isoreactivity, poor stability.Noble metal catalyst comprises the carrier used such as Pd, Pt, Rh, Ru, Au aluminium oxide, silica, ceria, molecular sieve etc.Although the catalytic performance of these catalyst is good, there is the shortcomings such as metal dispersity is low, catalyst cost is high, complicated process of preparation.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of material be made up of carrier and active metal component, and this metal component has polymolecularity in the carrier, and the effect being conducive to metal active constituent plays.
In order to realize above-mentioned technical purpose, the present inventor, through a large amount of exploratory development, adopts metallic organic framework (MOFs) material as carrier, by active metal component dispersion in the carrier.
MOFs material is a kind of novel porous material, is formed by metal and organoligand coordination, has adjustable topological structure and duct, the porosity of super large and specific area, receives people in recent years and pay close attention to widely.Therefore, the specific area of MOFs material super large is utilized to be expected to improve the decentralization of active component.
But, how active component is dispersed in this MOFs material? at present, generally adopt the method mixed with MOFs material by the presoma of active component, but the presoma of active metal component is difficult to enter in the duct of MOFs material.For this reason, the present inventor finds after a large amount of exploratory development, amino MOFs material is adopted to be carrier, adopt the metal precursor containing carbonyl, utilize the amino in MOFs material and the carbonyl generation complex reaction in metal precursor active metal component can be introduced in MOFs material, then realize the high degree of dispersion of active metal component in MOFs structure by reduction.
That is, this technical scheme is: a kind of amino MOFs material comprising active metal component, using amino MOFs material as carrier, by active metal component dispersion in the carrier, forms the amino MOFs material comprising active metal component.Wherein, as preferably, described active metal component quality accounts for 0.05% ~ 15% of amino MOFs quality of materials, and more preferably 0.2% ~ 10%.
Present invention also offers a kind of preparation method comprising the amino MOFs material of active metal component, comprise the steps:
By active metal predecessor, amino MOFs material, and organic solvent Homogeneous phase mixing, carbonyl is comprised in described active metal presoma, mixed solution is warming up to 45 ~ 110 DEG C, carbonyl in amino in MOFs material and active metal presoma reacts, and active metal presoma is connected on amino MOFs material; Reacted product is dry, then with reducing agent reduction, obtain the ammonobase organic framework material comprising active metal component.
As preferably, described amino MOFs material through vacuum drying treatment, to remove the water and organic solvent etc. in MOFs material.
As preferably, the temperature of described mixed solution is 50 ~ 105 DEG C.
As preferably, the described reaction time is 6 ~ 48 hours.
As preferably, described comprises in the amino MOFs material of active metal component, and active metal component quality accounts for 0.05% ~ 10% of amino MOFs quality of materials.
The amino in MOFs material do not limit by described amino MOFs material, comprises NH
2-MIL-101, NH
2-MIL-53, NH
2-CAU-1, and NH
2-UiO-66 etc.
Described active metal is not limit, and comprises platinum, palladium etc.
Namely described active metal presoma refers to the material comprising this active metallic element, comprises the acetate of corresponding active metal, acetylacetonate etc.
Described organic solvent is not limit, and comprises methyl alcohol, ethanol, toluene, acetone, chloroform etc.The easy dispersed active metal predecessor of acetone, and volatile, easily remove, therefore as preferably, described organic solvent is acetone.
Described reducing agent is not limit, and comprises sodium borohydride, hydrazine hydrate etc.
As preferably, the concentration of described reducing agent is 0.01 ~ 1M, more preferably 0.05 ~ 0.6M.
As preferably, the described recovery time is 0.5 ~ 12h, more preferably 1 ~ 6h.
In sum, the present invention with amino MOFs material for carrier, this carrier and the active metal presoma containing carbonyl are formed mixed solution, the carbonyl in the amino in MOFs material and active metal presoma is utilized to react, active metal presoma is connected on MOFs material, then realizes dispersed in MOFs structure of active metal component by reduction.This preparation method is simply controlled, can realize the high degree of dispersion of active metal on carrier.The method is easy to amplify preparation.
When the ammonobase organic framework material that this comprises active metal component is as catalyst, due to the high degree of dispersion of active component, its catalytic effect is remarkable.Such as, prepare in the technique of aromatic amine at aromatic nitro compound (comprising hydrogenation of chloronitrobenzene, p-nitrophenol etc.) hydrogenation catalyst hydrogenating reduction, when utilizing this catalyst, its catalytic effect is remarkable.
Accompanying drawing explanation
Fig. 1 is Pd/NH obtained in the embodiment of the present invention 1
2the transmission electron microscope photo of-UiO-66;
Fig. 2 is the Pd/NH in the embodiment of the present invention 1,2
2-UiO-66, Pd/NH
2-MIL-53 is used for the conversion ratio graph of a relation over time of nitrophenol when p-nitrophenol hydrogenating reduction prepares aniline as catalyst;
Fig. 3 is the Pd/NH in the embodiment of the present invention 3,4,5
2-MIL-101, Pt/NH
2-MIL-101, Pt/NH
2-MIL-53 is used for the conversion ratio graph of a relation over time of nitrobenzene when aniline is prepared in hydrogenation of chloronitrobenzene reduction as catalyst.
Detailed description of the invention
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1:
In this enforcement, active metal component is Pd, and ammonobase organic framework material is NH
2-UiO-66, the ammonobase organic framework material comprising this active metal component is designated as Pd/NH
2-UiO-66, wherein Pd quality accounts for NH
20.2 ~ 10wt% of-UiO-66 quality.
This Pd/NH
2the preparation method of-UiO-66 material is as follows:
(1) 0.2 ~ 10wt%Pd/NH is prepared
2-UiO-66:
NH
2the preparation method of-UiO-66 is as document: Nanoscale, described in 2013,5,9374-9382.
This NH
2-UiO-66 has good heat endurance and water stability, and specific surface reaches 950m
2g
-1above.By this NH
2-UiO-66 powder carries out vacuum drying treatment more than 12 hours in vacuum drying chamber at 150 DEG C.
(2) weigh the palladium of 2 ~ 110mg, being scattered in 45ml acetone, within ultrasonic 5 minutes, to being uniformly dispersed, obtaining the first solution.Meanwhile, the NH after 0.5g being activated
2-UiO-66 is scattered in 50ml acetone, ultrasonic to being uniformly dispersed, and obtains the second solution; First solution is mixed with the second solution, stirring at normal temperature 1 ~ 2h, then to load in Hydrothermal Synthesis still 75 DEG C of reactions 20 hours; By centrifugal for reacted product, oven dry.
(3) take 50mg hydrazine hydrate to be dissolved in 5mL deionized water, then add the powder that step (2) obtains, stirred at ambient temperature 3 hours, then centrifugal, vacuum drying, obtains Pd/NH
2-UiO-66.
The above-mentioned Pd/NH prepared
2as shown in Figure 1, as can be seen from the figure, active metal particles is uniformly distributed in the carrier the transmission electron microscope photo of-UiO-66, does not occur the phenomenon that active metal particles is reunited and piled up.
By the above-mentioned Pd/NH prepared
2-UiO-66 is used for p-nitrophenol hydrogenating reduction as catalyst and prepares in paranitroanilinum, and detailed process is as follows:
By this Pd/NH of 10mg
2-UiO-66 catalyst is scattered in 10mL p-nitrophenol (3mM), obtain mixed solution, then in cuvette, add this mixed solution of 0.1mL, then sodium borohydride (0.06M) solution adding 2.0mL deionized water and 1.0mL reacts, and is checked the concentration of p-nitrophenol by uv-vis spectra.
The conversion ratio of nitrophenol over time graph of a relation as shown in Figure 2, when being 15 minutes when reacted, p-nitrophenol conversion ratio reaches 85.3%.
Embodiment 2:
In the present embodiment, active metal component is Pd, and ammonobase organic framework material is NH
2-MIL-53, the ammonobase organic framework material comprising this active metal component is designated as Pd/NH
2-MIL-53, wherein Pd quality accounts for NH
20.2 ~ 10wt% of-MIL-53 quality.
This Pd/NH
2the preparation method of-MIL-53 material is as follows:
(1) Pd/NH is prepared
2-MIL-53:
NH
2-MIL-53 raw powder's production technology is as document: Inorganic Chemistry, described in 2009,48,3057-3064.
This NH
2-MIL-53 has higher specific area and aperture, has good heat endurance and water stability simultaneously.By this NH
2-MIL-53 powder carries out vacuum drying treatment more than 12 hours in vacuum drying chamber at 150 DEG C.
(2) palladium acetylacetonate of precise 3 ~ 150mg, is scattered in 50ml acetone, ultrasonic to being uniformly dispersed, and obtains the first solution; Meanwhile, the NH after 0.5g being activated
2-MIL-53 is dispersed in 50ml acetone, ultrasonic to being uniformly dispersed, and obtains the second solution; First solution is mixed with the second solution, stirring at normal temperature 1 ~ 2h, then to load in Hydrothermal Synthesis still 70 DEG C of reactions 12 hours; By centrifugal for reacted product, oven dry.
(3) take 37.8mg sodium borohydride to be dissolved in 5mL deionized water, then add the powder that step (2) obtains, stirred at ambient temperature 4 hours, then centrifugal, ethanol washing is also dry in ambient temperature in vacuum, obtains Pd/NH
2-MIL-53.
By the above-mentioned Pd/NH prepared
2-MIL-53 is used for p-nitrophenol hydrogenating reduction as catalyst and prepares in paranitroanilinum, and detailed process is substantially the same manner as Example 1, and difference uses Pd/NH
2-MIL-53 replaces Pd/NH
2-UiO-66.
The conversion ratio of p-nitrophenol over time graph of a relation as shown in Figure 2, be 15 minutes when reacted, p-nitrophenol conversion ratio reaches 82.3%.
Embodiment 3:
In this enforcement, active metal component is Pd, and ammonobase organic framework material is NH
2-MIL-101, the ammonobase organic framework material comprising this active metal component is designated as Pd/NH
2-MIL-101, wherein Pd quality accounts for NH
20.2 ~ 10wt% of-MIL-101 quality.
This Pd/NH
2the preparation method of-MIL-101 material is as follows:
(1) NH is prepared
2-MIL-101 powder
NH
2-MIL-101 raw powder's production technology is as document: RSC Advances, described in 2012,2,6417-6419.
This NH
2-MIL-101 powder has good heat endurance and water stability, and specific surface reaches 2500m
2g
-1above.By this NH
2-MIL-101 powder carries out vacuum drying treatment at 150 DEG C, to remove NH
2moisture content in-MIL-101 duct.
(2) weigh the palladium acetylacetonate of 3 ~ 150mg, be scattered in 50ml acetone, ultrasonic to being uniformly dispersed, obtain the first solution; Meanwhile, the NH after 0.5g being activated
2-MIL-101 is dispersed in 50ml acetone, ultrasonic to being uniformly dispersed, and obtains the second solution; First solution is mixed with the second solution, stirring at normal temperature 1 ~ 2h, then to load in Hydrothermal Synthesis still 70 DEG C of reactions 12 hours; By centrifugal for reacted product, oven dry;
(3) take 37.8mg sodium borohydride to be dissolved in 5mL deionized water, then add the powder that step (2) obtains, stirred at ambient temperature 4 hours, then centrifugal, ethanol washing is also dry in ambient temperature in vacuum, obtains Pd/NH
2-MIL-101.
By the above-mentioned Pd/NH prepared
2-MIL-101 is used for hydrogenation of chloronitrobenzene reduction as catalyst and prepares in aniline, and detailed process is as follows:
By this Pd/NH of 0.2g
2-MIL-101 catalyst mixes in a kettle. with 50mL absolute ethyl alcohol; Drive the air in reactor away with hydrogen after, start heat up and stir simultaneously; Temperature injects 2.5mL nitrobenzene after rising to 40 DEG C, reacts 2 hours.
By liquid sampling analysis after above-mentioned reaction, the conversion ratio of nitrobenzene over time relation as shown in Figure 3, be 2 constantly little when reacted, nitrobenzene conversion rate is 98.6%, and aniline is selective is 90.0%.
Embodiment 4:
In this enforcement, active metal component is Pt, and ammonobase organic framework material is NH
2-MIL-101, the ammonobase organic framework material comprising this active metal component is designated as Pt/NH
2-MIL-101, wherein Pt quality accounts for NH
20.2 ~ 10wt% of-MIL-101 quality.
This Pt/NH
2the preparation method of-MIL-101 material is as follows:
(1) NH is prepared
2-MIL-101 powder
This NH
2-MIL-101 raw powder's production technology is identical with the step (1) in embodiment 3.
This NH
2-MIL-101 powder has good heat endurance and water stability, and specific surface reaches 2500m
2g
-1above.By this NH
2-MIL-101 powder carries out vacuum drying treatment more than 12 hours at 150 DEG C.
(2) weigh the acetylacetone,2,4-pentanedione platinum of 2 ~ 110mg, being scattered in 50ml acetone, within ultrasonic 5 minutes, to being uniformly dispersed, obtaining the first solution; Meanwhile, the NH after 0.5g being activated
2-MIL-101 is scattered in 50ml acetone, ultrasonic to being uniformly dispersed, and obtains the second solution; First solution is mixed with the second solution, stirring at normal temperature 1 ~ 2h, then to load in Hydrothermal Synthesis still 50 DEG C of reactions 24 hours; By centrifugal for reacted product, oven dry.
(3) take 50mg sodium borohydride to be dissolved in 5mL deionized water, then add the powder that step (2) obtains, stirred at ambient temperature 6 hours, then centrifugal, ethanol washing is also dry in ambient temperature in vacuum, obtains Pt/NH
2-MIL-101.
By the above-mentioned Pt/NH prepared
2-MIL-101 is used for hydrogenation of chloronitrobenzene reduction as catalyst and prepares in aniline, and detailed process is substantially the same manner as Example 3, and difference uses Pt/NH
2-MIL-101 replaces Pd/NH
2-MIL-101, the reaction time is 2.5 hours.
By liquid sampling analysis after above-mentioned reaction, the conversion ratio of nitrobenzene over time relation as shown in Figure 3, be 2.5 constantly little when reacted, nitrobenzene conversion rate is 100%, and aniline is selective is 92.0%.
Embodiment 5:
In the present embodiment, active metal component is Pt, and ammonobase organic framework material is NH
2-MIL-53, the ammonobase organic framework material comprising this active metal component is designated as Pt/NH
2-MIL-53, wherein Pt quality accounts for NH
20.2 ~ 10wt% of-MIL-53 quality.
This Pt/NH
2the preparation method of-MIL-53 material is as follows:
(1) Pt/NH is prepared
2-MIL-53:
This NH
2synthesis, the activation of-MIL-53 are identical with embodiment 2;
(2) this step is substantially identical with the step (2) in embodiment 4, and difference uses NH
2-MIL-53 replaces NH
2-MIL-101.
(3) this step is identical with the step (3) in embodiment 4, obtains Pt/NH
2-MIL-101.
By the above-mentioned Pt/NH prepared
2-MIL-53 is used for hydrogenation of chloronitrobenzene reduction as catalyst and prepares in aniline, and detailed process is substantially the same manner as Example 3, and difference uses Pt/NH
2-MIL-53 replaces Pd/NH
2-MIL-101, the reaction time is 2.5 hours.
By liquid sampling analysis after above-mentioned reaction, the conversion ratio of nitrobenzene over time relation as shown in Figure 3, be 2.5 constantly little when reacted, nitrobenzene conversion rate is 99.5%, and aniline is selective is 89.0%.
Above-described embodiment has been described in detail technical scheme of the present invention and beneficial effect; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any amendments and improvement etc. made in spirit of the present invention, all should be included within protection scope of the present invention.
Claims (10)
1. one kind comprises the ammonobase organic framework material of active metal component, it is characterized in that: using ammonobase organic framework material as carrier, active metal component is dispersed in this carrier, and described active metal component quality accounts for 0.05% ~ 15% of amino MOFs quality of materials.
2. comprise the ammonobase organic framework material of active metal component as claimed in claim 1, it is characterized in that: described active metal component quality accounts for 0.2% ~ 10% of amino MOFs quality of materials.
3. comprise the ammonobase organic framework material of active metal component as claimed in claim 1, it is characterized in that: described amino MOFs material comprises NH
2-MIL-101, NH
2-MIL-53, NH
2-CAU-1 or NH
2-UiO-66.
4. comprise the ammonobase organic framework material of active metal component as claimed in claim 1, it is characterized in that: described active metal comprises platinum and/or palladium.
5. prepare the ammonobase organic framework material comprising active metal component in Claims 1-4 described in arbitrary claim, it is characterized in that: comprise the steps:
By active metal predecessor, amino MOFs material, and organic solvent Homogeneous phase mixing, carbonyl is comprised in described active metal presoma, mixed solution is warming up to 45 ~ 110 DEG C, carbonyl in amino in MOFs material and active metal presoma reacts, and active metal presoma is connected on amino MOFs material; Reacted product is dry, then with reducing agent reduction, obtain the ammonobase organic framework material comprising active metal component.
6. preparation as claimed in claim 5 comprises the method for the ammonobase organic framework material of active metal component, it is characterized in that: the temperature of described mixed solution is 50 ~ 105 DEG C; The described reaction time is preferably 6 ~ 48 hours.
7. preparation as claimed in claim 5 comprises the method for the ammonobase organic framework material of active metal component, it is characterized in that: described active metal presoma is acetate and/or the acetylacetonate of corresponding active metallic element; Described organic solvent is preferably one or more the mixing in methyl alcohol, ethanol, toluene, acetone, chloroform.
8. preparation as claimed in claim 5 comprises the method for the ammonobase organic framework material of active metal component, it is characterized in that: described reducing agent comprises one or more the mixing in sodium borohydride, hydrazine hydrate.
9. the application of ammonobase organic framework material as catalyst comprising active metal component as described in claim arbitrary in Claims 1-4.
10. the ammonobase organic framework material comprising active metal component as described in claim arbitrary in Claims 1-4 prepares aromatic amine as catalyst application in aromatic nitro compound hydrogenation catalyst hydrogenating reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410781464.0A CN104525264B (en) | 2014-12-16 | 2014-12-16 | Ammonobase organic framework material, its preparation method and application comprising active metal component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410781464.0A CN104525264B (en) | 2014-12-16 | 2014-12-16 | Ammonobase organic framework material, its preparation method and application comprising active metal component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104525264A true CN104525264A (en) | 2015-04-22 |
| CN104525264B CN104525264B (en) | 2017-08-25 |
Family
ID=52840997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410781464.0A Active CN104525264B (en) | 2014-12-16 | 2014-12-16 | Ammonobase organic framework material, its preparation method and application comprising active metal component |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104525264B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498844A (en) * | 2015-12-07 | 2016-04-20 | 辽宁师范大学 | In-situ preparation method and application of Ag/AgCl/NH2-MIL-101(Fe) composite photocatalyst with spindle appearance |
| CN105772092A (en) * | 2016-03-21 | 2016-07-20 | 中国科学技术大学 | Modified catalyst and preparation method thereof |
| CN105884642A (en) * | 2016-05-03 | 2016-08-24 | 蚌埠学院 | Amino-functionalization metal-organic framework nanocrystalline fluorescent material and preparation method and application thereof |
| CN106378194A (en) * | 2016-08-25 | 2017-02-08 | 山东师范大学 | Transition metal copper loaded UiO-66-NH2 composite catalyst, preparation method and application thereof |
| CN107486245A (en) * | 2017-09-18 | 2017-12-19 | 湖北大学 | A kind of NH2 MIL 125 for being catalyzed ammonia borane hydrolysis production hydrogen load silver-colored cobalt alloy nanocatalyst |
| CN107754861A (en) * | 2017-11-01 | 2018-03-06 | 中国科学院福建物质结构研究所 | A kind of preparation method and application of carbon quantum dot/metal organic framework catalyst |
| CN109054401A (en) * | 2018-07-12 | 2018-12-21 | 中南大学 | A kind of Uio-66/ poly aromatic amine composite material and preparation method and application with core-shell structure |
| CN111318294A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN111359670A (en) * | 2020-03-10 | 2020-07-03 | 浙江工业大学 | Au-Pd/NH2-MIL-101(Cr) catalyst and preparation and application thereof |
| CN112121863A (en) * | 2020-10-26 | 2020-12-25 | 广州大学 | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof |
| CN112547127A (en) * | 2020-12-22 | 2021-03-26 | 广东石油化工学院 | Composite catalyst for hydrogen production by catalytic pyrolysis of formic acid and preparation method and application thereof |
| CN112774662A (en) * | 2019-11-04 | 2021-05-11 | 北京氦舶科技有限责任公司 | Monoatomic catalyst, preparation method and application thereof |
| CN113559941A (en) * | 2021-08-24 | 2021-10-29 | 大连工业大学 | MOFs material-based metal nanoparticle-loaded catalyst and preparation method and application thereof |
| CN114177944A (en) * | 2021-11-24 | 2022-03-15 | 北京农学院 | Visible light catalytic degradation anabasine pesticide of metal organic framework compound |
| CN114621097A (en) * | 2022-03-29 | 2022-06-14 | 浙江解氏新材料股份有限公司 | Method for preparing 2, 4-difluoroaniline through catalytic hydrogenation of 2, 4-difluoronitrobenzene |
| CN115505130A (en) * | 2022-09-19 | 2022-12-23 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285891A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
| WO2012144758A2 (en) * | 2011-04-18 | 2012-10-26 | 한국화학연구원 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
-
2014
- 2014-12-16 CN CN201410781464.0A patent/CN104525264B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012144758A2 (en) * | 2011-04-18 | 2012-10-26 | 한국화학연구원 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN102285891A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
Non-Patent Citations (3)
| Title |
|---|
| LIJUAN SHEN ET AL: ""Highly dispersed palladium nanoparticles anchored on UiO-66(NH2) metal-organic framework as a reusable and dual functional visible-light-driven photocatalyst"", 《NANOSCALE》 * |
| MEIKE A.GOTTHARDT ET AL: ""Post-Synthetic Immobilization of Palladium Complexes on Metal-Organic Frameworks - A New Concept for the Design of Heterogeneous Catalysts for Heck Reactions"", 《RSC ADVANCES》 * |
| YUANBIAO HUANG ET AL: ""Facile synthesis of palladium nanoparticles encapsulated in amine-functionalized mesoporous metal–organic frameworks and catalytic for dehalogenation of aryl chlorides"", 《JOURNAL OF CATALYSIS》 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498844A (en) * | 2015-12-07 | 2016-04-20 | 辽宁师范大学 | In-situ preparation method and application of Ag/AgCl/NH2-MIL-101(Fe) composite photocatalyst with spindle appearance |
| CN105498844B (en) * | 2015-12-07 | 2018-04-20 | 辽宁师范大学 | Ag/AgCl/NH with spindle pattern2The in-situ preparation method of MIL 101 (Fe) composite photo-catalyst and the application of the catalyst |
| CN105772092B (en) * | 2016-03-21 | 2019-08-27 | 中国科学技术大学 | A kind of modified catalyst and preparation method thereof |
| CN105772092A (en) * | 2016-03-21 | 2016-07-20 | 中国科学技术大学 | Modified catalyst and preparation method thereof |
| CN105884642A (en) * | 2016-05-03 | 2016-08-24 | 蚌埠学院 | Amino-functionalization metal-organic framework nanocrystalline fluorescent material and preparation method and application thereof |
| CN105884642B (en) * | 2016-05-03 | 2018-03-27 | 蚌埠学院 | Nanocrystalline fluorescent material of metal-organic backbone of amino functional and its preparation method and application |
| CN106378194A (en) * | 2016-08-25 | 2017-02-08 | 山东师范大学 | Transition metal copper loaded UiO-66-NH2 composite catalyst, preparation method and application thereof |
| CN106378194B (en) * | 2016-08-25 | 2018-08-10 | 山东师范大学 | A kind of UiO-66-NH of carrying transition metal copper2Composite catalyst and the preparation method and application thereof |
| CN107486245A (en) * | 2017-09-18 | 2017-12-19 | 湖北大学 | A kind of NH2 MIL 125 for being catalyzed ammonia borane hydrolysis production hydrogen load silver-colored cobalt alloy nanocatalyst |
| CN107486245B (en) * | 2017-09-18 | 2020-08-07 | 湖北大学 | NH for catalyzing ammonia borane hydrolysis to produce hydrogen 2-MI L-125 supported silver-cobalt alloy nano catalyst |
| CN107754861A (en) * | 2017-11-01 | 2018-03-06 | 中国科学院福建物质结构研究所 | A kind of preparation method and application of carbon quantum dot/metal organic framework catalyst |
| CN109054401A (en) * | 2018-07-12 | 2018-12-21 | 中南大学 | A kind of Uio-66/ poly aromatic amine composite material and preparation method and application with core-shell structure |
| CN111318294A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN112774662A (en) * | 2019-11-04 | 2021-05-11 | 北京氦舶科技有限责任公司 | Monoatomic catalyst, preparation method and application thereof |
| CN112774662B (en) * | 2019-11-04 | 2023-08-15 | 北京氦舶科技有限责任公司 | Monoatomic catalyst and preparation method and application thereof |
| CN111359670A (en) * | 2020-03-10 | 2020-07-03 | 浙江工业大学 | Au-Pd/NH2-MIL-101(Cr) catalyst and preparation and application thereof |
| CN112121863A (en) * | 2020-10-26 | 2020-12-25 | 广州大学 | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof |
| CN112547127A (en) * | 2020-12-22 | 2021-03-26 | 广东石油化工学院 | Composite catalyst for hydrogen production by catalytic pyrolysis of formic acid and preparation method and application thereof |
| CN113559941A (en) * | 2021-08-24 | 2021-10-29 | 大连工业大学 | MOFs material-based metal nanoparticle-loaded catalyst and preparation method and application thereof |
| CN114177944A (en) * | 2021-11-24 | 2022-03-15 | 北京农学院 | Visible light catalytic degradation anabasine pesticide of metal organic framework compound |
| CN114621097A (en) * | 2022-03-29 | 2022-06-14 | 浙江解氏新材料股份有限公司 | Method for preparing 2, 4-difluoroaniline through catalytic hydrogenation of 2, 4-difluoronitrobenzene |
| CN114621097B (en) * | 2022-03-29 | 2024-03-15 | 浙江解氏新材料股份有限公司 | Method for preparing 2, 4-difluoroaniline by catalytic hydrogenation of 2, 4-difluoronitrobenzene |
| CN115505130A (en) * | 2022-09-19 | 2022-12-23 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104525264B (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104525264B (en) | Ammonobase organic framework material, its preparation method and application comprising active metal component | |
| Qiao et al. | Enhanced catalytic reduction of p-nitrophenol on ultrathin MoS2 nanosheets decorated with noble metal nanoparticles | |
| CN108097316B (en) | Preparation method of MOFs nano material loaded with nano metal particles | |
| CN102643513B (en) | Preparation method of meta-aminophenol-formaldehyde resin spheres and preparation method of carbon spheres | |
| CN103949286B (en) | A kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage | |
| CN101733094B (en) | Pt-CeO2/graphene electro-catalyst and preparation method thereof | |
| CN104841470A (en) | Composite titanium dioxide nano-sheet photocatalyst, preparation method and applications thereof | |
| CN110540984B (en) | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof | |
| WO2023274269A1 (en) | Noble metal-loaded covalent organic framework composite material, and preparation method therefor | |
| CN108499529B (en) | Active coke supported nano gold catalyst and preparation method and application thereof | |
| CN104600327B (en) | A kind of preparation method of carbon-supported nano platinum alloy catalyst | |
| CN106622224B (en) | Application of the nanometer Au-based catalyst in formic acid or formates synthesis | |
| CN104399535B (en) | The preparation method and application that a kind of magnetic partner is catalyst based | |
| CN104307512A (en) | Supported palladium catalyst and preparation method and application thereof | |
| CN103539596A (en) | Method for catalyzing transfer of hydrogen controllable reduction nitro-compound in formic acid or formate | |
| CN104857955A (en) | Method for preparing a noble metal nano catalyst | |
| CN108636433B (en) | Nitrogen-doped porous carbon immobilized noble metal catalyst and preparation method and application thereof | |
| CN103157494A (en) | Method of synthesizing Pt-Ni catalyst material by hydrothermal method | |
| CN113797936A (en) | Water phase preparation method and application of Pt-Cu alloy hollow nanospheres | |
| CN109453762A (en) | A kind of preparation method and application of modified clay mine loaded palladium catalyst | |
| CN110935481B (en) | Catalyst for selective hydrogenolysis of aromatic ether bond, preparation and application thereof | |
| CN103801296A (en) | Preparation method of nickel-based catalyst for syngas preparation by methane partial oxidation | |
| CN103145545A (en) | Method of preparing propanoldiacid through catalytic oxidation of glycerol | |
| CN113731441A (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN103736483B (en) | A kind of preparation method of the fuel cell platinum based catalyst of high activity high-durability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |