CN104525264B - Ammonobase organic framework material, its preparation method and application comprising active metal component - Google Patents
Ammonobase organic framework material, its preparation method and application comprising active metal component Download PDFInfo
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Abstract
The invention provides a kind of ammonobase organic framework material comprising active metal component.The material is using ammonobase organic framework material as carrier, and active metal component is dispersed in the carrier, and wherein active metal component quality accounts for the 0.05%~15% of amino MOFs quality of materials.The present invention forms mixed solution using by the carrier with the active metal presoma containing carbonyl, reacted using the amino in MOFs materials with the carbonyl in active metal presoma, active metal presoma is set to be connected on MOFs materials, then the material is prepared by the method for reduction, realizes active metal component dispersed in MOFs structures.When the material is as catalyst, due to the high degree of dispersion of active component, the technique that its catalytic effect significantly, for example prepares aromatic amine for aromatic nitro compound hydrogenating reduction is medium.
Description
Technical field
The present invention relates to the material being made up of carrier and active metal component, and in particular to one kind includes 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.And aromatic amine is then a kind of important change
Intermediate is learned, the industries such as pharmacy, plastics, printing and dyeing and Cosmetic Manufacture are widely used in.Therefore, people try to utilize fragrant nitre
Based compound prepares aromatic amine, mainly there is iron powder reducing method, electrolytic reduction and catalytic hydrogenation method at present.Wherein catalytic hydrogenation
The technique underproduction, pollute small therefore enjoy people's pro-gaze.
The key that catalytic hydrogenating reduction aromatic nitro compound prepares in aromatic amine technique is hydrogenation catalyst, efficient to add
Hydrogen catalyst is conducive to improving the conversion ratio of aromatic nitro compound and the selectivity of aromatic amine.The hydrogenation of current document report
Catalyst is broadly divided into non-precious metal catalyst and noble metal catalyst.Non-precious metal catalyst such as Ni, Co isoreactivity is low, stably
Property is poor.Carrier of the noble metal catalyst used in including Pd, Pt, Rh, Ru, Au etc. have aluminum oxide, silica, ceria, point
Son sieve etc..Although the catalytic performance of these catalyst is good, there is low metal dispersity, catalyst cost height, prepare work
The shortcomings of skill is complicated.
The content of the invention
For the above-mentioned state of the art, the present invention is intended to provide a kind of material being made up of carrier and active metal component, is somebody's turn to do
Metal component has polymolecularity in the carrier, is conducive to the effect of metal active constituent to play.
In order to realize above-mentioned technical purpose, the present inventor passes through a large amount of exploratory developments, using metal organic framework (MOFs)
Material is scattered in the carrier by active metal component as carrier.
MOFs materials are a kind of new porous materials, are formed by metal and organoligand coordination, with adjustable topology
Structure and duct, the porosity and specific surface area of super large, receive people and widely pay close attention in recent years.Therefore, MOFs materials are utilized
The specific surface area of material super large is expected to improve the decentralization of active component.
However, how active component is dispersed in the MOFs materialsAt present, it is general using by before active component
The method that body is mixed with MOFs materials is driven, but the presoma of active metal component is hardly entered in the duct of MOFs materials.For
This, the present inventor has found after a large amount of exploratory developments, amino MOFs materials is used for carrier, using the metal front containing carbonyl
Body, active metal component can be introduced by occurring complex reaction using the carbonyl in the amino and metal precursor in MOFs materials
In MOFs materials, high degree of dispersion of the active metal component in MOFs structures is then realized by reduction.
That is, the technical scheme is：A kind of amino MOFs materials comprising active metal component, using amino MOFs materials as
Carrier, active metal component is scattered in the carrier, form the amino MOFs materials for including active metal component.Wherein, as
It is preferred that, described active metal component quality accounts for the 0.05%~15% of amino MOFs quality of materials, more preferably 0.2%
~10%.
Present invention also offers a kind of preparation method of the amino MOFs materials comprising active metal component, including following step
Suddenly：
Active metal predecessor, amino MOFs materials, and organic solvent are uniformly mixed, described active metal forerunner
Carbonyl, the amino that mixed solution is warming up in 45~110 DEG C, MOFs materials and the carbonyl in active metal presoma are included in body
Base is reacted, and active metal presoma is connected on amino MOFs materials；Reacted product is dried, reducing agent is then used
Reduction, obtains including the ammonobase organic framework material of active metal component.
Preferably, the described vacuum dried processing of amino MOFs materials, to remove water in MOFs materials and organic
Solvent etc..
Preferably, the temperature of the mixed solution is 50~105 DEG C.
Preferably, the described reaction time is 6~48 hours.
Preferably, in the described amino MOFs materials comprising active metal component, active metal component quality accounts for ammonia
The 0.05%~10% of base MOFs quality of materials.
Described amino MOFs materials do not limit the amino in MOFs materials, including NH2-MIL-101、NH2-MIL-53、NH2-
CAU-1, and NH2- UiO-66 etc..
Described active metal is not limited, including platinum, palladium etc..
Described active metal presoma is to refer to the material for including the active metallic element, includes the vinegar of correspondence active metal
Hydrochlorate, acetylacetonate etc..
Described organic solvent is not limited, including methanol, ethanol, toluene, acetone, chloroform etc..Acetone easily disperses activity gold
Belong to predecessor, and volatile, easy removal, therefore preferably, described organic solvent is acetone.
Described reducing agent is not limited, including sodium borohydride, hydrazine hydrate etc..
Preferably, the concentration of the reducing agent is 0.01~1M, more preferably 0.05~0.6M.
Preferably, the described recovery time is 0.5~12h, more preferably 1~6h.
In summary, the present invention is using amino MOFs materials as carrier, by the carrier and the active metal presoma containing carbonyl
Mixed solution is formed, is reacted using the amino in MOFs materials with the carbonyl in active metal presoma, before active metal
Drive body to be connected on MOFs materials, then realize that active metal component is dispersed in MOFs structures by reduction.The system
Preparation Method is simply controllable, it is possible to achieve high degree of dispersion of the active metal on carrier.This method is easy to amplification and prepared.
When the ammonobase organic framework material comprising active metal component is as catalyst, due to active component
High degree of dispersion, its catalytic effect is notable.For example, in aromatic nitro compound (including hydrogenation of chloronitrobenzene, p-nitrophenol etc.) plus
Hydrogen catalysis hydrogenating reduction is prepared in the technique of aromatic amine, and during using the catalyst, its catalytic effect is notable.
Brief description of the drawings
Fig. 1 is obtained Pd/NH in the embodiment of the present invention 12- UiO-66 transmission electron microscope photo；
Fig. 2 is the Pd/NH in the embodiment of the present invention 1,22-UiO-66、Pd/NH2- MIL-53 is used for nitre as catalyst
The conversion ratio of nitrophenol changes with time graph of a relation when base phenol hydrogenation reduction prepares aniline；
Fig. 3 is the Pd/NH in the embodiment of the present invention 3,4,52-MIL-101、Pt/NH2-MIL-101、Pt/NH2-MIL-53
The conversion ratio for being used for nitrobenzene when hydrogenation of chloronitrobenzene reduction prepares aniline as catalyst changes with time graph of a relation.
Embodiment
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings, it should be pointed out that reality as described below
Apply example to be intended to be easy to the understanding of the present invention, and do not play any restriction effect to it.
Embodiment 1：
In this implementation, active metal component is Pd, and ammonobase organic framework material is NH2- UiO-66, includes the activity
The ammonobase organic framework material of metal component is designated as Pd/NH2- UiO-66, wherein Pd mass accounts for NH2- UiO-66 quality
0.2~10wt%.
The Pd/NH2The preparation method of-UiO-66 materials is as follows：
(1) 0.2~10wt%Pd/NH is prepared2-UiO-66：
NH2- UiO-66 preparation method such as document：Nanoscale, described in 2013,5,9374-9382.
The NH2- UiO-66 has good heat endurance and water stability, and 950m has been reached than surface2g-1More than.Should
NH2- UiO-66 powders carry out vacuum drying treatment more than 12 hours in vacuum drying chamber at 150 DEG C.
(2) 2~110mg palladium is weighed, is scattered in 45ml acetone, ultrasound obtains first in 5 minutes to being uniformly dispersed
Solution.Meanwhile, the NH after 0.5g is activated2- UiO-66 is scattered in 50ml acetone, and ultrasound obtains second molten to being uniformly dispersed
Liquid；First solution is mixed with the second solution, 1~2h of stirring at normal temperature, be then charged into Hydrothermal Synthesiss kettle 75 DEG C and react 20 hours；
By the centrifugation of reacted product, drying.
(3) 50mg hydrazine hydrates are weighed to be dissolved in 5mL deionized waters, the powder that step (2) is obtained is added, stirs at room temperature
Mix 3 hours, be then centrifuged for, be dried in vacuo, obtain Pd/NH2-UiO-66。
The above-mentioned Pd/NH prepared2- UiO-66 transmission electron microscope photo as shown in figure 1, it will be apparent from this figure that
Active metal particles are uniformly distributed in the carrier, the phenomenon that active metal particles are reunited and accumulated do not occur.
By the above-mentioned Pd/NH prepared2- UiO-66 is used for p-nitrophenol hydrogenating reduction as catalyst and prepared to nitre
In base aniline, detailed process is as follows：
By the 10mg Pd/NH2- UiO-66 catalyst is scattered in 10mL p-nitrophenols (3mM), obtains mixed solution,
Then the 0.1mL mixed solutions are added in cuvette, 2.0mL deionized waters and 1.0mL sodium borohydride is then added
(0.06M) solution is reacted, and the concentration of p-nitrophenol is checked by uv-vis spectra.
The conversion ratio of nitrophenol change with time graph of a relation as shown in Fig. 2 between when reacted be 15 minutes when, to nitre
Base phenol conversion reaches 85.3%.
Embodiment 2：
In the present embodiment, active metal component is Pd, and ammonobase organic framework material is NH2- MIL-53, includes the work
The ammonobase organic framework material of property metal component is designated as Pd/NH2- MIL-53, wherein Pd mass accounts for NH2- MIL-53 quality
0.2~10wt%.
The Pd/NH2The preparation method of-MIL-53 materials is as follows：
(1) Pd/NH is prepared2-MIL-53：
NH2- MIL-53 raw powder's production technologies such as document：Inorganic Chemistry, 2009,48,3057-3064
Described in.
The NH2- MIL-53 has higher specific surface area and aperture, while having good heat endurance and water stabilization
Property.By the NH2- MIL-53 powders carry out vacuum drying treatment more than 12 hours in vacuum drying chamber at 150 DEG C.
(2) 3~150mg of precise palladium acetylacetonate, is scattered in 50ml acetone, and ultrasound is obtained to being uniformly dispersed
First solution；Meanwhile, the NH after 0.5g is activated2- MIL-53 is dispersed in 50ml acetone, and ultrasound obtains the to being uniformly dispersed
Two solution；First solution is mixed with the second solution, 1~2h of stirring at normal temperature, be then charged into 70 DEG C of reactions 12 in Hydrothermal Synthesiss kettle
Hour；By the centrifugation of reacted product, drying.
(3) 37.8mg sodium borohydrides are weighed to be dissolved in 5mL deionized waters, the powder that step (2) is obtained, room temperature is added
Lower stirring 4 hours, is then centrifuged for, and ethanol is washed and is dried in vacuo at room temperature, obtains Pd/NH2-MIL-53。
By the above-mentioned Pd/NH prepared2- MIL-53 is used for p-nitrophenol hydrogenating reduction as catalyst and prepared to nitre
In base aniline, detailed process is substantially the same manner as Example 1, except that using Pd/NH2- MIL-53 replaces Pd/NH2-UiO-66。
The conversion ratio of p-nitrophenol changes with time graph of a relation as shown in Fig. 2 being 15 minutes between when reacted, to nitre
Base phenol conversion reaches 82.3%.
Embodiment 3：
In this implementation, active metal component is Pd, and ammonobase organic framework material is NH2- MIL-101, includes the work
The ammonobase organic framework material of property metal component is designated as Pd/NH2- MIL-101, wherein Pd mass accounts for NH2- MIL-101 quality
0.2~10wt%.
The Pd/NH2The preparation method of-MIL-101 materials is as follows：
(1) NH is prepared2- MIL-101 powders
NH2- MIL-101 raw powder's production technologies such as document：RSC Advances, described in 2012,2,6417-6419.
The NH2- MIL-101 powders have good heat endurance and water stability, and 2500m is reached than surface2g-1More than.
By the NH2- MIL-101 powders carry out vacuum drying treatment at 150 DEG C, to remove NH2Moisture content in-MIL-101 ducts.
(2) 3~150mg palladium acetylacetonate is weighed, is scattered in 50ml acetone, ultrasound obtains first to being uniformly dispersed
Solution；Meanwhile, the NH after 0.5g is activated2- MIL-101 is dispersed in 50ml acetone, and ultrasound obtains second molten to being uniformly dispersed
Liquid；First solution is mixed with the second solution, 1~2h of stirring at normal temperature, be then charged into Hydrothermal Synthesiss kettle 70 DEG C and react 12 hours；
By the centrifugation of reacted product, drying；
(3) 37.8mg sodium borohydrides are weighed to be dissolved in 5mL deionized waters, the powder that step (2) is obtained, room temperature is added
Lower stirring 4 hours, is then centrifuged for, and ethanol is washed and is dried in vacuo at room temperature, obtains Pd/NH2-MIL-101。
By the above-mentioned Pd/NH prepared2- MIL-101 is prepared in aniline as catalyst for hydrogenation of chloronitrobenzene reduction,
Detailed process is as follows：
By the 0.2g Pd/NH2- MIL-101 catalyst is mixed in a kettle. with 50mL absolute ethyl alcohols；Driven away instead with hydrogen
Answer after the air in kettle, start to warm up and stir simultaneously；Temperature rises to injection 2.5mL nitrobenzene after 40 DEG C, reacts 2 hours.
Liquid sampling after above-mentioned reaction is analyzed, the conversion ratio of nitrobenzene changes with time relation as shown in figure 3, when anti-
When being 2 hours between seasonable, nitrobenzene conversion rate is 98.6%, and aniline is selectively 90.0%.
Embodiment 4:
In this implementation, active metal component is Pt, and ammonobase organic framework material is NH2- MIL-101, includes the work
The ammonobase organic framework material of property metal component is designated as Pt/NH2- MIL-101, wherein Pt mass accounts for NH2- MIL-101 quality
0.2~10wt%.
The Pt/NH2The preparation method of-MIL-101 materials is as follows：
(1) NH is prepared2- MIL-101 powders
The NH2- MIL-101 raw powder's production technologies are identical with the step (1) in embodiment 3.
The NH2- MIL-101 powders have good heat endurance and water stability, and 2500m is reached than surface2g-1More than.
By the NH2- MIL-101 powders carry out vacuum drying treatment more than 12 hours at 150 DEG C.
(2) 2~110mg acetylacetone,2,4-pentanedione platinum is weighed, is scattered in 50ml acetone, ultrasound is obtained for 5 minutes to being uniformly dispersed
First solution；Meanwhile, the NH after 0.5g is activated2- MIL-101 is scattered in 50ml acetone, and ultrasound obtains the to being uniformly dispersed
Two solution；First solution is mixed with the second solution, 1~2h of stirring at normal temperature, be then charged into 50 DEG C of reactions 24 in Hydrothermal Synthesiss kettle
Hour；By the centrifugation of reacted product, drying.
(3) 50mg sodium borohydrides are weighed to be dissolved in 5mL deionized waters, the powder that step (2) is obtained are added, at room temperature
Stirring 6 hours, is then centrifuged for, and ethanol is washed and is dried in vacuo at room temperature, obtains Pt/NH2-MIL-101。
By the above-mentioned Pt/NH prepared2- MIL-101 is prepared in aniline as catalyst for hydrogenation of chloronitrobenzene reduction,
Detailed process is substantially the same manner as Example 3, except that using Pt/NH2- MIL-101 replaces Pd/NH2- MIL-101, during reaction
Between be 2.5 hours.
Liquid sampling after above-mentioned reaction is analyzed, the conversion ratio of nitrobenzene changes with time relation as shown in figure 3, when anti-
When being 2.5 hours between seasonable, nitrobenzene conversion rate is 100%, and aniline is selectively 92.0%.
Embodiment 5：
In the present embodiment, active metal component is Pt, and ammonobase organic framework material is NH2- MIL-53, includes the work
The ammonobase organic framework material of property metal component is designated as Pt/NH2- MIL-53, wherein Pt mass accounts for NH2- MIL-53 quality
0.2~10wt%.
The Pt/NH2The preparation method of-MIL-53 materials is as follows：
(1) Pt/NH is prepared2-MIL-53：
The NH2- MIL-53 synthesis, activation is identical with embodiment 2；
(2) step and step (2) in embodiment 4 are essentially identical, except that using NH2- MIL-53 replaces NH2-
MIL-101。
(3) step is identical with the step (3) in embodiment 4, obtains Pt/NH2-MIL-101。
By the above-mentioned Pt/NH prepared2- MIL-53 is prepared in aniline as catalyst for hydrogenation of chloronitrobenzene reduction,
Detailed process is substantially the same manner as Example 3, except that using Pt/NH2- MIL-53 replaces Pd/NH2- MIL-101, reaction time
For 2.5 hours.
Liquid sampling after above-mentioned reaction is analyzed, the conversion ratio of nitrobenzene changes with time relation as shown in figure 3, when anti-
When being 2.5 hours between seasonable, nitrobenzene conversion rate is 99.5%, and aniline is selectively 89.0%.
Technical scheme and beneficial effect are described in detail embodiment described above, it should be understood that
The specific embodiment of the present invention is the foregoing is only, is not intended to limit the invention, it is all to be done in the spirit of the present invention
Any modification and improvement etc., should be included in the scope of the protection.
Claims (7)
1. a kind of ammonobase organic framework material comprising active metal component, it is characterized in that：With ammonobase organic backbone
Material is as carrier, and active metal component is dispersed in the carrier, and described active metal component quality accounts for amino MOFs materials
The 0.05%~15% of quality；
The preparation method of the described ammonobase organic framework material comprising active metal component comprises the following steps：
Active metal predecessor, amino MOFs materials, and organic solvent are uniformly mixed, in described active metal presoma
Comprising carbonyl, the amino that mixed solution is warming up in 45~110 DEG C, MOFs materials is sent out with the carbonyl in active metal presoma
Raw reaction, active metal presoma is connected on amino MOFs materials；Reacted product is dried, then with reducing agent also
Original, obtains including the ammonobase organic framework material of active metal component；
Described active metal is platinum；
Described amino MOFs materials are NH2-MIL-101、NH2-MIL-53、NH2- CAU-1 or NH2-UiO-66；
Described active metal presoma is the acetate and/or acetylacetonate of correspondence active metallic element.
2. the ammonobase organic framework material as claimed in claim 1 for including active metal component, it is characterized in that：Described
Active metal component quality accounts for the 0.2%~10% of amino MOFs quality of materials.
3. the ammonobase organic framework material as claimed in claim 1 for including active metal component, it is characterized in that：It is described mixed
The temperature for closing solution is 50~105 DEG C.
4. the ammonobase organic framework material as claimed in claim 1 for including active metal component, it is characterized in that：Described
Reaction time is 6~48 hours.
5. the ammonobase organic framework material as claimed in claim 1 for including active metal component, it is characterized in that：Described
Organic solvent is mixing more than one or both of methanol, ethanol, toluene, acetone, chloroform.
6. the ammonobase organic framework material as claimed in claim 1 for including active metal component, it is characterized in that：Described
Reducing agent includes mixing more than one or both of sodium borohydride, hydrazine hydrate.
7. the ammonobase organic backbone material comprising active metal component as described in any claim in claim 1 to 6
Material prepares aromatic amine as catalyst applied to aromatic nitro compound hydrogenation catalyst hydrogenating reduction.
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| 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 |
| CN112121863B (en) * | 2020-10-26 | 2022-10-04 | 广州大学 | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof |
| CN112547127B (en) * | 2020-12-22 | 2022-11-29 | 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 |
| 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 |
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