CN106916110B - Supported noble metal nanoparticle composite material and preparation method thereof - Google Patents
Supported noble metal nanoparticle composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106916110B CN106916110B CN201710141586.7A CN201710141586A CN106916110B CN 106916110 B CN106916110 B CN 106916110B CN 201710141586 A CN201710141586 A CN 201710141586A CN 106916110 B CN106916110 B CN 106916110B
- Authority
- CN
- China
- Prior art keywords
- noble metal
- organic framework
- metal
- composite material
- zif
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a supported noble metal nanoparticle composite material and a preparation method thereof, and particularly relates to a metal organic framework supported noble metal nanoparticle composite material with stable chemical properties and a preparation method thereof. The noble metal nanoparticles in the composite material have uniform particle size and narrow distribution range, and are all 3-4 nm. The composite material is obtained by taking inorganic noble metal acid as a precursor, selecting a metal organic framework which has stable chemical properties and cannot be corroded by aqueous solution of the inorganic noble metal acid in the preparation process as a carrier and combining a specific wet impregnation and in-situ reduction method. The method has the advantages of simple and quick operation and mild conditions, and can control the exposed crystal face of the noble metal nano particles in the obtained compound to be the face-centered cubic fcc (111) crystal face, so that the method has wide application prospect.
Description
Technical Field
The invention belongs to the field of nanoparticle preparation, relates to a supported noble metal nanoparticle composite material and a preparation method thereof, and particularly relates to a metal organic framework supported noble metal nanoparticle composite material and a method for simply and quickly preparing the composite material by taking a metal organic framework with stable chemical properties as a carrier and an inorganic noble metal acid as a precursor and adopting an impregnation combined in-situ reduction method.
Background
Metal Organic Frameworks (MOFs) are a Metal Organic framework structure material with high specific surface area, ordered porosity, certain chemical and thermal stability, which has been widely studied in recent years as a novel material and mainly applied to the fields of separation, energy storage, drug delivery, catalysis, etc. Among them, ZIF-67, a zeolitic MOF, has attracted considerable attention in the field of material synthesis because it combines the excellent properties of MOF and zeolite.
Great progress has been made in the synthesis of MOF supported metal nanoparticles. Many synthetic methods have been explored to synthesize such materials, and in the prior literature, the method reported in the literature that precious metal nanoparticles are supported by MOF generally uses a relatively expensive organic precious metal precursor, and the in-situ reduction method is reduction under hydrogen high-temperature conditions. Part of the system also needs to be added with a stabilizing agent. The methods are complicated in preparation, high in cost and harsh in reaction conditions, and the metal nanoparticles in the obtained product generally have the problems of poor uniformity, too wide particle size distribution range and agglomeration among the nanoparticles.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a supported noble metal nanoparticle composite material and a preparation method thereof. The method of the invention can stably and uniformly distribute the noble metal nano particles such as Pd, Pt, Au and the like on the metal organic framework, and keep narrow particle size distribution, smaller particle size (3 nm-4 nm) and monodispersity. Moreover, the method is simple and rapid to operate and mild in condition, and can control the exposed crystal face of the noble metal nano particle in the obtained compound to be the face-centered cubic fcc (111) crystal face.
In a first aspect, the invention provides a supported noble metal nanoparticle composite material, which comprises a carrier and noble metal nanoparticles supported on the carrier, wherein the carrier is a metal-organic framework, the noble metal nanoparticles are stably supported on the metal-organic framework carrier, the particle size is small and uniform, the particle size is between 3nm and 4nm, and the distribution range is narrow.
In the composite material of the present invention, the particle size of the noble metal nanoparticles is 3nm to 4nm, such as 3nm, 3.1nm, 3.2nm, 3.3nm, 3.4nm, 3.5nm, 3.7nm or 4nm, and the specific values between the above values are limited by space and for the sake of brevity, and the present invention is not exhaustive of the specific values included in the ranges.
Preferably, the noble metal nanoparticles are in a uniform monodisperse state.
As a preferred technical solution of the supported noble metal nanoparticle composite material of the present invention, the noble metal nanoparticles in the composite material are obtained by reducing an aqueous solution of an inorganic noble metal acid with a reducing agent, and the reduction is preferably an in-situ reduction.
In the present invention, the term "inorganic noble metal acid" means: the inorganic acid containing a noble metal element is, for example, chloroauric acid, chloropalladite, chloroplatinic acid, or the like.
In the present invention, it is necessary to ensure that the metal organic framework is stable in the aqueous solution of the inorganic noble metal acid and does not corrode during the reduction process.
The preferred metal organic framework employed in the present invention is ZIF-67. ZIF-67 is a zeolite-type metal organic framework with excellent chemical stability and thermal stability, which is not corroded by aqueous solution of inorganic noble metal acid and has stable structure when used in the process of preparing the composite material.
Preferably, the noble metal nanoparticles include any one or a combination of at least two of Pd, Pt, or Au, but are not limited to the above-listed substances, and other noble metal nanoparticles commonly used in the art may also be used in the present invention.
Preferably, the mass percentage content of the noble metal nanoparticles is 3.3 wt% to 10.2 wt%, such as 3.3 wt%, 3.5 wt%, 3.7 wt%, 4.0 wt%, 4.5 wt%, 4.75 wt%, 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.3 wt%, 6.6 wt%, 7.0 wt%, 7.5 wt%, 8.0 wt%, 8.5 wt%, 9.0 wt%, 9.5 wt%, or 10.0 wt%, etc., based on 100 wt% of the total mass of the supported noble metal nanoparticle composite.
As a preferred technical scheme of the supported noble metal nanoparticle composite material, the invention provides a ZIF-67 supported noble metal nanoparticle composite material. In the composite material, noble metal nanoparticles having a particle diameter of 3 to 4nm are stably and uniformly supported on a carrier of ZIF-67 in a monodisperse state.
In a second aspect, the present invention provides a method for preparing a supported noble metal nanoparticle composite material according to the first aspect, the method comprising the steps of:
(1) preparing an aqueous solution of inorganic noble metal acid;
(2) adding an aqueous solution of inorganic noble metal acid into a suspension of a purple metal organic framework for impregnation;
(3) and (3) dissolving a reducing agent in a solvent, adding the obtained dispersion liquid into the impregnation system obtained after the impregnation in the step (2), and stirring to change the color of the system from purple to black to obtain the supported noble metal nanoparticle composite material.
Preferably, the molar concentration of the inorganic noble metal acid in the aqueous solution of the inorganic noble metal acid in the step (1) is 35 mM-70 mM, and preferably 50 mM.
Preferably, the inorganic noble metal acid includes any one or a combination of at least two of chloropalladic acid, chloroplatinic acid, or chloroauric acid, but is not limited to the above-listed inorganic noble metal acids, and other inorganic noble metal acids commonly used in the art may also be used in the present invention.
In the method of the present invention, the metal-organic framework in the aqueous solution of the inorganic noble metal acid and the suspension of the metal-organic framework in step (2) is not corroded in order to ensure that a composite material comprising a metal-organic framework support and noble metal nanoparticles supported on the support can be obtained, and the metal-organic framework is preferably ZIF-67 and/or ZIF-8, and particularly preferably ZIF-67.
The ZIF-67 and/or ZIF-8 refers to: can be ZIF-67, ZIF-8, or a mixture of ZIF-67 and ZIF-8.
Preferably, the suspension of the metal-organic framework in step (2) is obtained by dissolving a powder of the metal-organic framework in a solvent.
Preferably, the mass-volume concentration of the metal-organic framework powder relative to the solvent is (15-20) mg/10mL, for example, 15mg/10mL, 16mg/10mL, 18mg/10mL, 19mg/10mL, or 20mg/10mL, and preferably 20mg/10 mL.
Preferably, in the process of preparing the suspension of the metal organic framework in the step (2), the solvent is water and/or an organic solvent, preferably an organic solvent, and further preferably methanol.
Preferably, in the process of preparing the suspension of the metal organic framework in the step (2), ultrasound is also accompanied, and the time of ultrasound is preferably 5min to 20min, for example, 5min, 6min, 8min, 10min, 13min, 15min, 20min, and the like, and more preferably 10 min.
Preferably, the volume ratio of the aqueous solution of the inorganic noble metal acid and the suspension of the metal-organic framework in the step (2) is 1:100 to 1:20, for example, 1:100, 1:90, 1:80, 1:70, 1:60, 1:55, 1:50, 1:40, 1:300, or 1: 20.
Preferably, the adding mode of the step (2) is dropwise adding, and the dropwise adding is preferably slow.
Preferably, the dropping rate is 30 to 60 drops per minute.
Preferably, the impregnation in step (2) is accompanied by stirring, and the stirring time is preferably 3h to 8h, for example, 3h, 4h, 5h, 6h, 7h or 8h, and preferably 6 h.
Preferably, the reducing agent in step (3) includes any one or a combination of two of sodium borohydride and hydrazine hydrate, but is not limited to the above-listed substances, and other reducing agents commonly used in the art can also be used in the present invention.
Preferably, the solvent in step (3) is water and/or an organic solvent, preferably an organic solvent, more preferably methanol, and particularly preferably cooled methanol.
Preferably, the dissolving of the reducing agent in the solvent in the step (3) is accompanied by ultrasound, and the time of the ultrasound is preferably 10s to 30s, preferably 10 s.
Preferably, in step (3), the mass-volume concentration of the reducing agent relative to the solvent is (3 to 10)1mg/mL, for example, 3mg/1mL, 3.5mg/1mL, 4mg/1mL, 4.2mg/1mL, 4.6mg/1mL, 5mg/1mL, 5.3mg/1mL, 5.5mg/1mL, 6mg/1mL, 6.5mg/1mL, 7mg/1mL, 7.5mg/1mL, 8mg/1mL, 8.5mg/1mL, 9mg/1mL, or 10mg/1mL, and preferably 7.2mg/1 mL.
Preferably, the volume ratio of the dispersion liquid in the step (3) to the impregnation system obtained after the impregnation in the step (2) is 1.05:1 to 1.30:1, for example, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.23:1, 1.25:1, 1.28:1, or 1.30: 1.
Preferably, the stirring time in step (3) is 0.5h to 2h, for example 0.5h, 1h, 1.2h, 1.5h or 2h, etc., preferably 1 h.
As a preferable technical scheme of the method, the method further comprises the steps of separating, washing and drying after the stirring in the step (3) is finished.
The separation according to the invention can be carried out by separation means customary in the art, such as filtration or centrifugation, preferably centrifugation, and the supernatant obtained.
Preferably, the rotation speed of the centrifugation is 600rpm to 1000rpm, preferably 8000 rpm.
Preferably, the time of centrifugation is 10 min.
Preferably, the number of washing is 3.
Preferably, the drying is carried out under light-shielding conditions;
preferably, the temperature of the drying is room temperature, preferably 25 ℃.
The "room temperature" as used herein means 20 to 30 ℃ such as 20 ℃, 22 ℃, 24 ℃,25 ℃, 26 ℃, 27 ℃ or 30 ℃.
Preferably, the drying time is preferably 12 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a composite material consisting of a metal organic framework carrier and noble metal nanoparticles loaded on the carrier, wherein the noble metal nanoparticles in the composite material have small particle size and narrow distribution range which are all between 2nm and 4nm, and the noble metal nanoparticles such as palladium, platinum, gold and the like are stably combined with the metal organic framework carrier, have good dispersibility and present a very good monodispersion state.
(2) The invention provides a method for simply, quickly and mildly preparing a supported noble metal nanoparticle composite material, which adopts inorganic noble metal acid as a precursor, adopts a metal organic framework which has stable chemical properties and cannot be corroded by aqueous solution of the inorganic noble metal acid in the preparation process as a carrier, synthesizes the composite material by wet impregnation and in-situ reduction technology, and can control the exposed crystal face of the noble metal nanoparticle in the obtained composite to be a face-centered cubic fcc (111) crystal face.
(3) The invention selects the inorganic noble metal acid as the precursor to prepare the load-type noble metal nano particle composite material, has the advantages of low price and easy obtainment compared with the conventional organic precursor, and the preparation method of the invention has the advantages of simplicity, rapidness, mild conditions and easy realization of industrial production.
Drawings
FIG. 1 is a TEM photograph of the ZIF-67 supported palladium nanoparticle composite material prepared in example 1 of the present invention.
FIG. 2 is a high-resolution TEM (transmission electron microscope) photograph of the ZIF-67 supported palladium nanoparticle composite material prepared in example 1 of the present invention.
FIG. 3 is a TEM photograph of the ZIF-67 loaded Pt nanoparticle composite material prepared in example 2 of the present invention.
FIG. 4 is a high-resolution TEM (transmission electron microscope) photograph of the ZIF-67 loaded Pt nanoparticle composite material prepared in example 2 of the present invention.
FIG. 5 is a TEM photograph of the ZIF-67 loaded Au nanoparticle composite material prepared in example 3 of the present invention.
FIG. 6 is a high-resolution TEM (transmission electron microscope) photograph of the ZIF-67 loaded Au nanoparticle composite material prepared in example 3 of the present invention.
FIG. 7 is a TEM photograph of the ZIF-8 supported palladium nanoparticle composite material prepared in example 4 of the present invention.
FIG. 8 is a high-resolution TEM (transmission electron microscope) photograph of the ZIF-8 supported palladium nanoparticle composite material prepared in example 4 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
First, ZIF-67 was prepared according to the literature (Li, H.; Ma, H.; Wang, X.; Gao, J.; Chen, C.; Shi, S.; Qu, M.; Feng, N.; Xu, J. journal of Energy Chemistry 2014,23, 742). Weighing 20mg of ZIF-67 powder, dissolving in 10ml of methanol, and ultrasonically dissolving for 10min to obtain a purple suspension system. 50mM aqueous chloropalladate solution was prepared. The aqueous solution of chloropalladate (300. mu.L) was removed by a pipette, slowly dropped into the ZIF-67 methanol solution system (i.e., the above-mentioned purple suspension system), and stirred for 6 hours to complete the impregnation process. Weighing 7.2mg of sodium borohydride, dissolving the sodium borohydride in 1ml of cooled methanol, ultrasonically dissolving the sodium borohydride for 10s, and adding the obtained dispersion into the impregnation system which is completely impregnated, wherein the system is changed from purple to black. Stirring was continued for 1h, followed by centrifugation at 8000rpm for 10min, separation of the clear solution and repeated washing with methanol 3 times. And drying the samples at room temperature for 12h in a dark place to obtain the ZIF-67 supported palladium nanoparticle composite material which is named as ZIF-67@ Pd NP.
And (3) performing characterization analysis on the obtained product ZIF-67 supported palladium nanoparticle composite material by adopting a transmission electron microscope and a high-resolution transmission electron microscope, wherein the transmission electron microscope is shown in figure 1, and the high-resolution transmission electron microscope is shown in figure 2.
From the characterization results, the chloropalladate is reduced to be converted into palladium nanoparticles growing on the ZIF-67 in situ. From the results of transmission electron microscopy characterization of FIG. 1, the palladium nanoparticles supported on ZIF-67 have very good dispersibility and uniform particle size distribution, with the particle size being 3.5 nm. + -. 0.5nm (where. + -. 0.5nm represents the statistical deviation); from the high resolution transmission electron microscope results shown in FIG. 2, the exposed crystal planes of the palladium nanoparticles can be controlled by using ZIF-67 as a carrier in combination with the method of the present invention, wherein the interplanar spacing is 0.23nm, which corresponds to fcc (111) crystal planes of palladium.
Example 2
ZIF-67 was prepared in the same manner as in example 1. Weighing 20mg of ZIF-67 powder, dissolving in 10ml of methanol, and ultrasonically dissolving for 10min to obtain a purple suspension system. 50mM chloroplatinic acid aqueous solution was prepared. The 300. mu.L of the chloroplatinic acid aqueous solution was transferred by a pipette, slowly dropped into the ZIF-67 methanol solution system (i.e., the above-mentioned purple suspension system), and stirred for 6 hours to complete the dipping process. Weighing 7.2mg of sodium borohydride, dissolving the sodium borohydride in 1ml of cooled methanol, ultrasonically dissolving the sodium borohydride for 10s, and adding the obtained dispersion into the impregnation system which is completely impregnated, wherein the system is changed from purple to black. Stirring was continued for 1h, followed by centrifugation at 8000rpm for 10min, separation of the clear solution and repeated washing with methanol 3 times. And drying the samples at room temperature for 12h in a dark place to obtain the ZIF-67 loaded platinum nanoparticle composite material which is named as ZIF-67@ Pt NP.
And (3) performing characterization analysis on the obtained product ZIF-67 loaded platinum nanoparticle composite material by adopting a transmission electron microscope and a high-resolution transmission electron microscope, wherein the transmission electron microscope is shown in figure 3, and the high-resolution transmission electron microscope is shown in figure 4.
From the characterization results, the chloroplatinic acid is reduced and then converted into the platinum nanoparticles growing on the ZIF-67 in situ. From the results of transmission electron microscopy characterization of fig. 3, it is seen that the platinum nanoparticles loaded on ZIF-67 have very good dispersibility and uniform particle size distribution, with the particle size being 3.3nm ± 0.5nm (where ± 0.5nm represents the statistical deviation); from the results of the high-resolution transmission electron microscope of FIG. 4, ZIF-67 as a carrier can control the exposed lattice planes of the platinum nanoparticles, the interplanar spacing is 0.23nm, corresponding to the fcc (111) lattice plane of platinum.
Example 3
First, ZIF-67 was prepared in the same manner as in example 1. Weighing 20mg of ZIF-67 powder, dissolving in 10ml of methanol, and ultrasonically dissolving for 10min to obtain a purple suspension system. A50 mM aqueous solution of chloroauric acid was prepared. Transferring 300 μ L of the chloroauric acid aqueous solution by a pipette, slowly dropping into ZIF-67 methanol solution system (i.e. the purple suspension system), and stirring for 6h to complete the impregnation process. Weighing 7.2mg of sodium borohydride, dissolving the sodium borohydride in 1ml of cooled methanol, ultrasonically dissolving the sodium borohydride for 10s, and adding the obtained dispersion into the impregnation system which is completely impregnated, wherein the system is changed from purple to black. Stirring was continued for 1h, followed by centrifugation at 8000rpm for 10min, separation of the clear solution and repeated washing with methanol 3 times. And drying the samples at room temperature for 12h in a dark place to obtain the ZIF-67 loaded gold nanoparticle composite material which is named as ZIF-67@ Au NP.
And (3) performing characterization analysis on the obtained product ZIF-67 loaded gold nanoparticle composite material by adopting a transmission electron microscope and a high-resolution transmission electron microscope, wherein the transmission electron microscope is shown in figure 5, and the high-resolution transmission electron microscope is shown in figure 6.
According to the characterization result, the chloroauric acid is reduced and then converted into gold nanoparticles growing on the ZIF-67 in situ. From the results of transmission electron microscopy characterization of fig. 1, gold nanoparticles loaded on ZIF-67 have very good dispersibility and uniform particle size distribution, with the particle size being 3.3nm ± 0.5nm (where ± 0.5nm represents statistical deviation); from the results of the high resolution transmission electron microscope shown in FIG. 2, ZIF-67 as a carrier can control the exposed lattice planes of gold nanoparticles, the interplanar spacing is 0.23nm, corresponding to the fcc (111) lattice plane of gold.
Example 4
First, ZIF-8 was prepared according to the literature (Torad, N.L.; Hu, M.; Kamachi, Y.; Takai, K.; Imura, M.; Naito, M.; Yamauchi, Y.chemical communications 2013,49, 2521). Weighing 20mg of ZIF-8 powder, dissolving in 10ml of methanol, and ultrasonically dissolving for 15min to obtain a milky white suspension system. 50mM aqueous chloropalladate solution was prepared. Using a pipette to remove 500 mu L of the chloropalladate aqueous solution, slowly dripping the chloropalladate aqueous solution into a ZIF-67 methanol solution system (namely the milky white suspension system), and stirring for 6 hours to complete the impregnation process to obtain a light yellow system. Weighing 10mg of sodium borohydride, dissolving the sodium borohydride in 1ml of cooled methanol, ultrasonically dissolving the sodium borohydride for 10s, and adding the obtained dispersion into the impregnation system which is completely impregnated, wherein the system is changed from light yellow to black. Stirring was continued for 1h, followed by centrifugation at 6000rpm for 10min, separation of the clear solution and repeated washing with methanol 3 times. And drying the samples at room temperature for 12h in a dark place to obtain the ZIF-8 supported palladium nanoparticle composite material which is named as ZIF-8@ Pd NP.
And (3) performing characterization analysis on the obtained product ZIF-8 loaded palladium nanoparticle composite material by adopting a transmission electron microscope and a high-resolution transmission electron microscope, wherein the transmission electron microscope is shown in figure 7, and the high-resolution transmission electron microscope is shown in figure 8.
According to the characterization result, the chloropalladate is reduced and then converted into the palladium nano particles growing on the ZIF-8 in situ. From the results of transmission electron microscopy characterization of fig. 7, the palladium nanoparticles supported on ZIF-8 have very good dispersibility and uniform particle size distribution, with the particle size being 3.3nm ± 0.5nm (where ± 0.5nm represents the statistical deviation); from the high resolution transmission electron microscope results of FIG. 8, it can be seen that the exposed crystal planes of the palladium nanoparticles can be controlled by using ZIF-8 as the carrier in combination with the method of the present invention, the interplanar spacing is 0.23nm, corresponding to the fcc (111) crystal plane of palladium.
Example 5
First, ZIF-67 was prepared in the same manner as in example 1. Weighing 15mg of ZIF-67 powder, dissolving in 10ml of methanol, and ultrasonically dissolving for 10min to obtain a purple suspension system. 60mM aqueous chloroauric acid solution was prepared. Transferring 300 μ L of the chloroauric acid aqueous solution by a pipette, dripping 60 drops of the chloroauric acid aqueous solution into a ZIF-67 methanol solution system (namely the purple suspension system) at a speed of 60 drops per minute, stirring for 3 hours, and adding the finished dispersion into the impregnated system, wherein the system is changed from purple to black. The dipping process was continued with stirring. Weighing 7.2mg sodium borohydride, dissolving in 2ml cooled methanol, ultrasonic dissolving for 10s to obtain 2h, centrifuging at 8000rpm for 6min, separating clear liquid, and repeatedly washing with methanol for 3 times. And drying the samples at room temperature for 12h in a dark place to obtain the ZIF-67 loaded gold nanoparticle composite material which is named as ZIF-67@ Au NP.
The product of this example was characterized and it was found from the results that chloroauric acid was reduced to gold nanoparticles grown in situ on ZIF-67. From the characterization result of a transmission electron microscope, the gold nanoparticles loaded on the ZIF-67 have very good dispersibility and uniform particle size distribution, and the particle size is 3.3nm +/-0.5 nm (wherein +/-0.5 nm represents the statistical deviation); from the result of a high-resolution transmission electron microscope, ZIF-67 as a carrier can control the exposed crystal planes of gold nanoparticles, the interplanar spacing is 0.23nm, and the interplanar spacing corresponds to fcc (111) crystal planes of gold.
Comparative example 1
The preparation method and conditions were the same as in example 2 except that the ZIF-67 was replaced with MOF-525.
In the preparation process of the comparative example, after the inorganic noble metal acid is added, the MOF-525 is immediately decomposed, so that the MOF-525 supported platinum nanoparticle composite material cannot be obtained.
Comparative example 2
The preparation method and conditions were the same as in example 2, except that the following operations were carried out after completion of the impregnation process: drying the impregnated precursor at room temperature (20-30 deg.C) for 12h in dark place, placing in a magnetic boat, placing in a tube furnace, heating at 5-10 deg.C/min, heating at 230 deg.C for 3h, introducing 10% volume fraction hydrogen/helium gas, and controlling flow rate at 5 ml/min.
The product prepared by the comparative example is characterized, and the result shows that all the loaded noble metals are seriously agglomerated and the nano particles cannot be obtained.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (30)
1. A preparation method of a supported noble metal nanoparticle composite material is characterized by comprising the following steps:
(1) preparing an aqueous solution of inorganic noble metal acid, wherein the molar concentration of the inorganic noble metal acid is 35 mM-70 mM;
(2) dropping an aqueous solution of inorganic noble metal acid into a suspension of a metal organic framework at a rate of 30-60 drops per minute for impregnation, wherein the suspension of the metal organic framework is obtained by dissolving metal organic framework powder in an organic solvent, the mass volume concentration of the metal organic framework powder relative to the solvent is (15-20) mg/10mL, the inorganic noble metal acid comprises any one or a combination of at least two of chloropalladate, chloroplatinic acid or chloroauric acid, and the metal organic framework is ZIF-67 and/or ZIF 8;
the volume ratio of the aqueous solution of the inorganic noble metal acid to the suspension of the metal organic framework is 1: 100-1: 20;
(3) dissolving a reducing agent in an organic solvent, adding the obtained dispersion liquid into the impregnation system obtained after the impregnation in the step (2), and stirring to obtain the supported noble metal nanoparticle composite material;
the reducing agent is any one or the combination of two of sodium borohydride and hydrazine hydrate;
in the step (3), the mass volume concentration of the reducing agent relative to the organic solvent is (3-10) 1mg/mL, and the volume ratio of the dispersion liquid in the step (3) to the impregnation system obtained after the impregnation in the step (2) is 1.05: 1-1.30: 1.
2. The method according to claim 1, wherein the inorganic noble metal acid is present in the aqueous solution of the inorganic noble metal acid in step (1) at a molar concentration of 50 mM.
3. The method of claim 1, wherein the aqueous solution of the inorganic noble metal acid of step (2) does not corrode the metal-organic framework in the suspension of the metal-organic framework.
4. The method of claim 1, wherein the metal organic framework is ZIF-67.
5. The method of claim 1, wherein the mass-to-volume concentration of the metal-organic framework powder relative to the solvent is 20mg/10 mL.
6. The method according to claim 1, wherein the organic solvent is methanol during the preparation of the suspension of the metal-organic framework in step (2).
7. The method according to claim 1, wherein ultrasound is also accompanied in the process of preparing the suspension of the metal-organic framework in the step (2).
8. The method of claim 7, wherein the time of the ultrasound is 5min to 20 min.
9. The method of claim 8, wherein the ultrasound is performed for a period of 10 min.
10. The method of claim 1, wherein the impregnating of step (2) is accompanied by agitation.
11. The method of claim 10, wherein the stirring time is 3 to 8 hours.
12. The method of claim 11, wherein the stirring time is 6 hours.
13. The method according to claim 1, wherein the organic solvent in step (3) is methanol.
14. The method of claim 13, wherein the organic solvent of step (3) is cooled methanol.
15. The method according to claim 1, wherein the dissolving of the reducing agent in the solvent in the step (3) is accompanied by sonication.
16. The method of claim 15, wherein the ultrasound is performed for a time period of 10s to 30 s.
17. The method of claim 16, wherein the ultrasound is for a time of 10 s.
18. The method according to claim 1, wherein in step (3), the mass volume concentration of the reducing agent relative to the solvent is 7.2mg/1 mL.
19. The method of claim 1, wherein the stirring time in step (3) is 0.5 to 2 hours.
20. The method of claim 19, wherein the stirring of step (3) is carried out for a period of 1 hour.
21. The method of claim 1, further comprising the steps of separating, washing and drying after the stirring of step (3) is completed.
22. The method of claim 21, wherein the separating is by: centrifuging and separating to obtain clear liquid.
23. The method of claim 22, wherein the centrifugation is at a speed of 600rpm to 1000 rpm.
24. The method of claim 23, wherein the centrifugation is performed at 8000 rpm.
25. The method of claim 22, wherein the time for centrifugation is 10 min.
26. The method of claim 21, wherein the number of washes is 3.
27. The method of claim 21, wherein the drying is performed under exclusion of light.
28. The method of claim 21, wherein the drying temperature is 20 ℃ to 30 ℃.
29. The method of claim 28, wherein the drying temperature is 25 ℃.
30. The method of claim 21, wherein the drying time is 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710141586.7A CN106916110B (en) | 2017-03-10 | 2017-03-10 | Supported noble metal nanoparticle composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710141586.7A CN106916110B (en) | 2017-03-10 | 2017-03-10 | Supported noble metal nanoparticle composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106916110A CN106916110A (en) | 2017-07-04 |
| CN106916110B true CN106916110B (en) | 2020-03-24 |
Family
ID=59460637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710141586.7A Active CN106916110B (en) | 2017-03-10 | 2017-03-10 | Supported noble metal nanoparticle composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106916110B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185525B (en) * | 2017-05-23 | 2020-04-28 | 重庆交通大学 | Octahedral Pt nanoparticle loaded gamma-Al2O3Process for preparing form catalyst |
| CN109647381B (en) * | 2017-10-12 | 2020-08-28 | 中国科学院福建物质结构研究所 | Method for controllably preparing highly-dispersed mesoporous carbon-based composite material of platinum particles as efficient hydrogen production electrocatalyst |
| CN107607525A (en) * | 2017-10-19 | 2018-01-19 | 北京市理化分析测试中心 | The metal organic framework and preparation method and application of supported precious metal nano-particle |
| CN107837820A (en) * | 2017-11-21 | 2018-03-27 | 南京工业大学 | A kind of preparation method of two-dimentional MOFs material loads nano-particle |
| CN108554454B (en) * | 2018-03-12 | 2019-11-15 | 华南理工大学 | A kind of metal-organic framework materials being fixed with Platinum Nanoparticles prepare purification process and its application |
| CN108586872A (en) * | 2018-05-07 | 2018-09-28 | 壹见传媒有限公司 | A kind of high intensity roof lamp |
| CN109179398B (en) * | 2018-10-24 | 2021-01-15 | 国家纳米科学中心 | Noble metal oxide nano composite material, preparation method and application thereof |
| CN110420666A (en) * | 2019-05-29 | 2019-11-08 | 东南大学 | The method of class zeolitic imidazolate framework material confinement preparation high dispersive palladium sub-nanometer grain |
| CN111342070B (en) * | 2020-04-16 | 2021-09-07 | 吉林省源田能源科技服务有限公司 | High-performance low-Pt-loading fuel cell oxygen reduction catalyst and preparation method thereof |
| CN111569928B (en) * | 2020-05-12 | 2021-07-20 | 武汉理工大学 | MOFs-derived carbon-based material anchored high-dispersion metal Pt nanocluster and preparation method and application thereof |
| CN112457676B (en) * | 2020-10-11 | 2021-09-21 | 北京科技大学 | Preparation method of metal organic framework/precious metal simple substance nanocomposite |
| CN113171455A (en) * | 2021-04-13 | 2021-07-27 | 浙江大学 | Metal organic framework nano particle with subcellular organelle targeting acoustodynamic combined chemotherapy anti-tumor function and preparation method thereof |
| CN114324863B (en) * | 2022-01-05 | 2023-01-17 | 云南大学 | Staphylococcus aureus toxin detection biological probe based on optical/electric double signal mode, and immunosensor and detection method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
| CN105879919A (en) * | 2016-04-26 | 2016-08-24 | 福州大学 | Au/ZIF-8-TiO2 catalyst and preparation method and application thereof |
| CN106040302A (en) * | 2016-06-23 | 2016-10-26 | 南京工业大学 | Hydrogenation catalyst |
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
-
2017
- 2017-03-10 CN CN201710141586.7A patent/CN106916110B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
| CN105879919A (en) * | 2016-04-26 | 2016-08-24 | 福州大学 | Au/ZIF-8-TiO2 catalyst and preparation method and application thereof |
| CN106040302A (en) * | 2016-06-23 | 2016-10-26 | 南京工业大学 | Hydrogenation catalyst |
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| Hollow Zn/Co ZIF Particles Derived from Core–Shell ZIF-67@ZIF-8 as Selective Catalyst for the Semi-Hydrogenation of Acetylene;Jian Yang,等;《Angew. Chem. Int. Ed.》;20150805;第54卷;10889-10893 * |
| Kui Shen，等.MOFs-Templated Co@Pd Core−Shell NPs Embedded in N‑Doped Carbon Matrix with Superior Hydrogenation Activities.《ACS Catal.》.2015,第5卷5264-5271. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106916110A (en) | 2017-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106916110B (en) | Supported noble metal nanoparticle composite material and preparation method thereof | |
| Hatamifard et al. | Green synthesis of a natrolite zeolite/palladium nanocomposite and its application as a reusable catalyst for the reduction of organic dyes in a very short time | |
| CN109453773B (en) | Supported bimetallic core-shell structure catalyst and preparation method thereof | |
| Liu et al. | Supported palladium nanoparticles: an efficient catalyst for the direct formation of H2O2 from H2 and O2 | |
| EP2254692B1 (en) | Method for preparing dispersions of precious metal nanoparticles and for isolating such nanoparticles from said dispersions | |
| CN100428989C (en) | Method for preparing loading type nano Pd/C catalyst from colloidal solution | |
| CN1970143A (en) | Method for preparing high-activity hydrogenation catalyst nano Ru/C | |
| Li et al. | Catalytic activity of shaped platinum nanoparticles for hydrogenation: a kinetic study | |
| Lin et al. | Flower-like ZnO-assisted one-pot encapsulation of noble metal nanoparticles supported catalysts with ZIFs | |
| US9957168B2 (en) | Method for synthesis of ruthenium nanoparticles with face-centered cubic and hexagonal close-packed structures | |
| CN101469139B (en) | Preparation of silicon oxide supported monodisperse nanoparticle nano complex | |
| Li et al. | Synthesis of monodisperse palladium nanoclusters using metal–organic frameworks as sacrificial templates | |
| Shen et al. | Highly dispersed silver nanoparticles confined in a nitrogen-containing covalent organic framework for 4-nitrophenol reduction | |
| CN113600181B (en) | Preparation method of nano palladium supported catalyst | |
| CN101616736B (en) | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal | |
| TWI617353B (en) | Manufacturing method of nano colloidal particle carrier and carrier thereof | |
| Janssen et al. | Separating Growth from Nucleation for Facile Control over the Size and Shape of Palladium Nanocrystals | |
| CN108610489B (en) | Preparation method of nano material based on metal organic framework material and with different dimensions | |
| JP5818007B2 (en) | Metal nanoparticle / polyimide composite fine particle and method for producing the same | |
| CN110153410B (en) | Method for growing ordered Pd array rod-like nanoparticles on surface of Au triangular plate and application of ordered Pd array rod-like nanoparticles | |
| Liu et al. | New perspective of a nano-metal preparation pathway based on the hexahydro-closo-hexaborate anion | |
| JP2013040358A (en) | Method for manufacturing metal porous body | |
| CN107737947B (en) | Preparation method of graphene platinum silver metal nanocomposite | |
| CN116586623B (en) | In-situ co-reduction preparation method of copper-based medium-entropy alloy nano material | |
| CN111686759B (en) | Preparation method of supported NiPd bimetallic catalyst and application of supported NiPd bimetallic catalyst in dehalogenation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |