CN113150301A - Hierarchical porous metal organic framework material containing Cu, Fe and Pd and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a hierarchical pore metal organic framework material containing Cu, Fe and Pd, and a preparation method and application thereof2+Substitution of CUS with Fe2+，Pd2+Replacement of part of Cu2+Of Fe2+，Pd2+Introduced into metal nodes of the HKUST-1 frame, and the prepared hierarchical pore metal organic frame material containing Cu, Fe and Pd comprises Cu-Cu, Cu-Fe, Fe-Fe, Cu-Pd,Fe-Pd and/or Pd-Pd and the like in a paddle-shaped structure and simultaneously form mesopores, the material contains a hierarchical pore structure, can be further used as a heterogeneous catalyst, remarkably improves the catalytic efficiency, and is widely applied to the fields of gas storage and separation, biology, catalysis and the like.
Description
Technical Field
The invention relates to the technical field of metal organic framework materials, in particular to a hierarchical pore metal organic framework material containing Cu, Fe and Pd and a preparation method and application thereof.
Background
The Metal Organic Frameworks (MOFs) material has novel physical and chemical properties and has wide application prospects in a plurality of fields such as gas storage and separation, biology, catalysis and the like. And the pore channel structure and the chemical composition of the MOFs material have certain adjustable designability, for example, the MOFs material with proper pore channel size and chemical composition can be designed for specific application targets in the modes of organic ligand coordination mode design, guest nanoparticle loading inclusion, mixed metal introduction, defect ligand introduction and the like. Copper-based HKUST-1([ Cu ]3(BTC)2]Is a classical structure in a plurality of MOFs, and a large amount of Coordinatively Unsaturated (CUS) Cu is contained in a metal node2+Site (Cu)2+CUS) and a microporous structure. However, mixed metal and hierarchical pore structures can be introduced into HKUST-1 through a certain synthetic design strategy.
At present, the regulation and control of the pore channels of the HKUST-1 structure to adapt to substrates with different sizes and the atomic/subnanometer level modification of metal nodes still have great challenges. Polymetallic HKUST-1 showed better performance relative to the original monometallic HKUST-1. In 2015, a bimetallic MOFs material MCu-BTC (M ═ Mn, Fe, Co) was reported by Dorina f. In 2016, Wenhua Zhang et al synthesized Pd by hydrothermal method0@[(Cu3-xPdx(BTC)2]nComposite material, a portion of Cu at a node of a frame2+-CUS by Pd2+-a CUS replacement of the mobile terminal,with part of Pd0The nano particles are loaded on a CuPd-HKUST-1 framework, and all the nano particles show more excellent performance than a mother structure of pure copper. Chinese patent CN107837823A discloses a magnetic hierarchical pore metal organic framework catalyst and a preparation method and application thereof, wherein the magnetic hierarchical pore metal organic framework catalyst is prepared by adding copper nitrate and trimesic acid into magnetic macroporous polyacrylamide, the structure contains Cu and Fe, but the catalytic effect is still poor. Such as replacing Cu with multiple metals2+E.g. using Fe2+，Pd2 +With simultaneous replacement of part of Cu2+Due to Fe2+，Pd2+The metal is equal to Cu2+Similar effective ionic radii and coordination habits, but for kinetic reasons, among others, the synthesis of multiwell HKUST-1 containing CuFePd trimetal remains a challenging task.
Disclosure of Invention
The invention aims to overcome the defect and the defect of the existing metal-doped hierarchical pore HKUST-1 catalyst that the catalytic performance is not ideal enough, and provides a preparation method of a hierarchical pore metal organic framework material containing Cu, Fe and Pd, which can not only use Fe2+And Pd2+The material is introduced to the metal nodes of the HKUST-1 framework, and simultaneously forms mesopores, and the material contains a hierarchical pore structure and is used as a catalyst, so that the catalytic activity is obviously improved.
The invention further aims to provide a hierarchical porous metal-organic framework material containing Cu, Fe and Pd.
The invention also aims to provide application of the hierarchical porous metal-organic framework material containing Cu, Fe and Pd.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a hierarchical porous metal organic framework material containing Cu, Fe and Pd comprises the following steps:
dissolving a copper salt, a ferrous salt and a palladium salt in a solvent to obtain a tri-metal salt solution containing the copper salt, the ferrous salt and the palladium salt, adding an organic ligand into the solution, and uniformly mixing; then placing the mixture at 50-80 ℃ for reaction for 8-13 hours, and naturally cooling the mixture to room temperature after the reaction is finished; centrifugally separating to obtain a solid product, and washing to obtain the hierarchical porous metal organic framework material containing Cu, Fe and Pd; wherein the molar ratio of the trimetal salt to the organic ligand is 1.3: 1.0-1.7: 1.0.
The method controls the proportion of copper salt, ferrous salt, palladium salt and organic ligand and the reaction temperature and time to carry out Cu at a metal node2+Substitution of CUS with Fe2+，Pd2+Replacement of part of Cu2+Comprises a plurality of paddle-shaped structures such as Cu-Cu, Cu-Fe, Fe-Fe, Cu-Pd, Fe-Pd and/or Pd-Pd and the like, and not only leads Fe to be2+And Pd2+The catalyst is introduced to the metal nodes of the HKUST-1 framework, simultaneously has mesopores formed, contains a hierarchical pore structure, and is used as a further heterogeneous catalyst, so that the catalytic efficiency of the catalyst is obviously improved.
Preferably, the molar ratio of the copper salt, the ferrous salt, the palladium salt and the organic ligand is 1.5: 1.0-1.7: 1.0.
Preferably, the organic ligand is 1,3, 5-trimesic acid and/or acetic acid. Meanwhile, the heterogeneous catalysis efficiency can be obviously improved by virtue of the formation of a coordination regulator, namely acetate and mesopores.
Preferably, the reaction temperature is 60-80 ℃.
Preferably, the solvent is one of ethanol, water and N, N-dimethylacetamide.
Preferably, the copper salt is Cu (NO)3)2、Cu(Ac)2、CuCl2One or more of them.
Preferably, the ferrous salt is FeCl2、FeSO4、Fe(Ac)2One or more of them.
Preferably, the palladium salt is Pd (NO)3)2And/or Pd (Ac)2。
Preferably, the washing is performed 5 times by using a mixed solution of ethanol and water, and unreacted precursors are removed, followed by 3 times by using acetone.
The invention protects the hierarchical pore metal organic framework material containing Cu, Fe and Pd prepared by the preparation method, and the chemical formula is [ Cu ]3-x-yFexPdy(BTC)2]nWherein 0.03<x<0.09,0.03<y<0.09。
The invention also protects the application of the hierarchical porous metal organic framework material containing Cu, Fe and Pd in the fields of gas storage and separation, biology and catalysis.
Compared with the prior art, the invention has the beneficial effects that:
the invention realizes the Cu at the metal node by regulating and controlling the ratio of the metal salt to the organic ligand and the reaction temperature and time2+Substitution of CUS with Fe2+，Pd2+Replacement of part of Cu2+Of Fe2+，Pd2+The prepared hierarchical pore metal organic framework material containing Cu, Fe and Pd comprises various paddle-shaped structures such as Cu-Cu, Cu-Fe, Fe-Fe, Cu-Pd, Fe-Pd and/or Pd-Pd and the like, and simultaneously forms mesopores, and the material contains the hierarchical pore structure, can be further used as a heterogeneous catalyst, remarkably improves the catalytic efficiency, and is widely applied to the fields of gas storage and separation, biology, catalysis and the like.
Drawings
FIG. 1(a) shows N in Compound 42Adsorption-desorption curves and pore size distribution curves and (b) N as parent HKUST-12Adsorption-desorption curves and pore size distribution curves.
FIG. 2 is a scanning electron micrograph of Compound 4.
FIGS. 3(a) to (f) are schematic diagrams of the two-core metal paddle wheel structures of compounds 1 to 4.
FIG. 4 is a powder diffraction pattern of compounds 1-4.
FIG. 5 is a graph of the conversion of parent HKUST-1 and Compound 4, respectively, as catalysts.
FIG. 6 is a schematic structural diagram of a hierarchical porous metal organic framework material containing Cu, Fe and Pd.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of a hierarchical porous metal organic framework material containing Cu, Fe and Pd comprises the following steps:
adding metal precursor Cu (NO)3)2·3H2O、Cu(Ac)2·H2O、FeSO4、FeCl2·4H2O、Pd(NO3)2(about 1.50mmol in total), placing the mixture into a polytetrafluoroethylene reaction kettle lining, immediately adding about 12mL of analytically pure DMA, and then stirring for 1.5 hours to completely dissolve all metal salts at room temperature to obtain a trimetal ion solution; then 1.00mmol of ligand H3Adding BTC into the trimetal ion solution, continuing stirring for about 2 hours to completely dissolve the BTC at room temperature, then sealing the polytetrafluoroethylene reaction kettle by using a stainless steel shell, heating the reaction kettle in an oven at 50 ℃ for 13 hours, finally taking out the reaction kettle, naturally cooling to room temperature, and collecting a product by centrifugation. Then, the mixture was washed 5 times with a mixture of ethanol and water (1: 1 by volume) to remove unreacted precursors. Then, the solvent exchange is carried out for 2 times by acetone, and finally, the HKUST-1 with the multilevel pores containing Cu, Fe and Pd is obtained by centrifugal separation and named as a compound 1, and the yield is about 60 percent. Phase purity was characterized via powder XRD (fig. 4).
Example 2
A preparation method of a hierarchical porous metal organic framework material containing Cu, Fe and Pd comprises the following steps:
metal precursor CuCl2·2H2O、Cu(Ac)2·H2O、FeSO4、Fe(Ac)2、Pd(Ac)2(ca. 1.50mmol total), placed in the teflon reactor liner, and about 12mL of analytically pure DMA added immediately, followed by stirring for about 1.5 hours to allow complete dissolution of all metal salts at room temperature to give a trimetallic ion solution. Then 1.00mmol of ligand H3BTC was added to the above trimetal ion solution and stirring was continued for 2 hours to completely dissolve it at room temperature. Subsequently, the Teflon reactor was sealed with a stainless steel metal shell and placed at 80 deg.CReaction 8 was heated in an oven. And finally, taking out the reaction kettle, naturally cooling to room temperature, collecting a product by centrifugation, washing the product for 5 times by using a mixed solution of ethanol and water (in a volume ratio of 1:1) to remove unreacted precursors, performing solvent exchange for 2 times by using acetone, and finally, obtaining the trimetallic hierarchical-pore HKUST-1 compound 2 by centrifugal separation, wherein the yield is about 54 percent. Phase purity was characterized via powder XRD (fig. 4).
Example 3
A preparation method of a hierarchical porous metal organic framework material containing Cu, Fe and Pd comprises the following steps:
metal precursor CuCl2·2H2O、Cu(Ac)2·H2O、FeCl2·4H2O、Fe(Ac)2、Pd(NO3)2(ca. 1.50mmol total), placed in the teflon reactor liner, added immediately about 12mL of analytically pure DMA, and stirred for 1.5 hours to completely dissolve all metal salts at room temperature to give a trimetallic ion solution. Then 1.00mmol of ligand H3BTC was added to the above trimetal ion solution and stirring was continued for 2 hours to completely dissolve it at room temperature. And then, sealing the polytetrafluoroethylene reaction kettle by using a stainless steel shell, placing the reaction kettle in an oven at 60 ℃ for heating reaction for 8-13 hours, finally, taking out the reaction kettle, naturally cooling to room temperature, and collecting a product by centrifugation. Then, the mixture was washed 5 times with a mixture of ethanol and water (1: 1 by volume) to remove unreacted precursors. Then solvent exchange is carried out for 2 times by acetone, and finally, the trimetallic hierarchical pore HKUST-1 compound 3 is obtained by centrifugal separation, and the yield is about 63 percent. Phase purity was characterized via powder XRD (fig. 4).
Example 4
A preparation method of a hierarchical porous metal organic framework material containing Cu, Fe and Pd comprises the following steps:
adding metal precursor Cu (NO)3)2·3H2O、Cu(Ac)2·H2O、Fe(Ac)2、FeCl2·4H2O、Pd(Ac)2(total about 1.50mmol) and charging into the inner lining of a polytetrafluoroethylene reaction kettleAbout 12mL of analytically pure DMA was immediately added and then stirred for 1.5 hours to completely dissolve all metal salts at room temperature to give a trimetallic ion solution. Then 1.00mmol of ligand H3BTC was added to the above trimetal ion solution and stirring was continued for 2.0 hours to completely dissolve it at room temperature. Subsequently, the Teflon reaction kettle is sealed by a stainless steel shell and is placed in an oven at 70 ℃ for heating reaction for 8 to 13 hours. And finally, taking out the reaction kettle, naturally cooling to room temperature, and collecting a product through centrifugation. Then, the mixture was washed 5 times with a mixture of ethanol and water (1: 1 by volume) to remove unreacted precursors. Then solvent exchange is carried out for 2 times by acetone, and finally, the trimetallic hierarchical-pore HKUST-1 compound 4 is obtained by centrifugal separation, and the yield is about 57 percent. Phase purity was characterized via powder XRD (fig. 4).
Comparative example 1
Cu(NO3)2·3H2O (about 1.50mmol) and H3BTC (about 1.00mmol) was charged into the inner liner of a polytetrafluoroethylene reaction vessel, about 14mL of analytically pure DMA was immediately added, followed by stirring for 2.0 hours to mix well, and subsequently, the polytetrafluoroethylene reaction vessel was sealed with a stainless steel metal shell and placed in an oven at 80 ℃ for heating reaction for 15 hours. And finally, taking out the reaction kettle, naturally cooling to room temperature, and collecting a product through centrifugation. Then, the mixture was washed 5 times with a mixture of ethanol and water (1: 1 by volume) to remove unreacted precursors. Then solvent exchange is carried out for 2 times by acetone, and finally, microporous HKUST-1 (parent HKUST-1) containing only Cu is obtained by centrifugal separation, and the yield is about 70%.
Performance testing
Taking Compound 4 as an example, the BET specific surface area (1690 m)2·g-1) The pore size distribution (coexistence of micropores and mesopores) is shown in FIG. 1(a), and the particle size (1 to 7 μm) is shown in FIG. 2. The structure of the hierarchical pore metal organic framework material containing Cu, Fe and Pd prepared by the invention can be seen from figure 6, and the structure can be seen more vividly in the figure. While the parent HKUST-1 of comparative example 1 (FIG. 1(b)) had micropores, no mesopores, and a specific surface area of 1780m2·g-1Only contains a wheel paddle structure of Cu-Cu.
As shown in FIGS. 3(a) to (f), the compounds 1 to 4 contain various paddle-like structures such as Cu-Cu, Cu-Fe, Fe-Fe, Cu-Pd, Fe-Pd and/or Pd-Pd.
The phase purity of the hierarchical pore metal organic framework materials containing Cu, Fe and Pd prepared in examples 1-4 is characterized by powder diffraction, as shown in FIG. 4, the diffraction peak of the test sample is consistent with the simulated diffraction peak signal, no extra diffraction peak is formed, and no extra phase is generated.
Taking the selective oxidation of benzyl alcohol to prepare benzaldehyde as an example, the reaction conditions for preparing benzaldehyde by the solid-liquid phase catalytic oxidation of benzyl alcohol are as follows: TBHP in an amount of 35mg of catalyst, benzyl alcohol in an amount of 50mg, benzyl alcohol and the like, acetonitrile in an amount of 5mL, a temperature of 80 ℃, and 6bar O2The atmosphere was stirred at 800rpm for 9 hours. The results are shown in FIG. 5, in which the conversion rate was about 15.5% using the parent HKUST-1 as the catalyst, and about 60% using the compound 4 as the catalyst. The catalytic reaction efficiency is improved by more than 3 times. The Fe and Pd dissimilar metal doping introduced on the metal nodes of the HKUST-1 framework and the formation of the multilevel pores are proved to have remarkable effects on improving the heterogeneous catalytic performance of the material.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a hierarchical pore metal organic framework material containing Cu, Fe and Pd is characterized by comprising the following steps:
dissolving a copper salt, a ferrous salt and a palladium salt in a solvent to obtain a tri-metal salt solution containing the copper salt, the ferrous salt and the palladium salt, adding an organic ligand into the solution, and uniformly mixing; then placing the mixture at 50-80 ℃ for reaction for 8-13 hours, and naturally cooling the mixture to room temperature after the reaction is finished; centrifugally separating to obtain a solid product, and washing to obtain the hierarchical porous metal organic framework material containing Cu, Fe and Pd; wherein the molar ratio of the trimetal salt to the organic ligand is 1.3: 1.0-1.7: 1.0.
2. The preparation method according to claim 1, wherein the molar ratio of the copper salt, the ferrous salt, the palladium salt and the organic ligand is 1.5: 1.0-1.7: 1.0.
3. The method according to claim 1 or 2, wherein the organic ligand is 1,3, 5-trimesic acid and/or acetic acid.
4. The method according to claim 1, wherein the reaction temperature is 60 to 80 ℃.
5. The method according to claim 1, wherein the solvent is one of ethanol, water, and N, N-dimethylacetamide.
6. The method according to claim 1, wherein the copper salt is Cu (NO)3)2、Cu(Ac)2、CuCl2One or more of them.
7. The method according to claim 1, wherein the ferrous salt is FeCl2、FeSO4、Fe(Ac)2One or more of them.
8. The method according to claim 1, wherein the palladium salt is Pd (NO)3)2And/or Pd (Ac)2。
9. The hierarchical porous metal organic framework material containing Cu, Fe and Pd prepared by the preparation method of any one of claims 1 to 8, which is characterized by having a chemical formula of [ Cu [ ]3-x-yFexPdy(BTC)2]nWherein 0.03<x<0.09,0.03<y<0.09。
10. The use of the hierarchical pore metal organic framework material containing Cu, Fe, Pd according to claim 9 in the fields of gas storage and separation, biology, catalysis.
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