CN110665498B - Preparation and application of noble metal-loaded magnetic nano stirrer catalyst - Google Patents
Preparation and application of noble metal-loaded magnetic nano stirrer catalyst Download PDFInfo
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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Abstract
The invention provides a preparation method of a magnetic nano stirrer catalyst loaded with noble metal, which comprises the following steps: (1) dispersing a magnetic nano stirrer in water, adding a noble metal solution, and mixing to obtain a noble metal precursor solution; (2) reducing the noble metal precursor under the action of a reducing agent to prepare the magnetic nano stirrer catalyst loaded with noble metal. The preparation method is simple, and the obtained noble metal-loaded magnetic nano stirrer has a one-dimensional chain structure, and the size, the structure and the catalyst components of the stirrer are adjustable. The invention also provides application of the catalyst, and the magnetic nano stirrer catalyst shows excellent catalytic effect through a p-nitrophenol model reaction, has paramagnetism and can be magnetically separated and recovered.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material synthesis and noble metal catalysis, and particularly relates to preparation and application of a noble metal-loaded magnetic nano stirrer catalyst.
Background
The one-dimensional magnetic nano material opens up a new direction for the preparation, functionalization and compound research of novel nano materials, and has potential application prospect in the fields of self-assembly, catalysis, sensors and the like. The one-dimensional magnetic nanochain can be prepared by magnetic field induced self-assembly, template induced self-assembly, dipole induced self-assembly and the like. The magnetic field induced self-assembly operation is simple, and after the one-dimensional magnetic nano-chain is assembled, the surface of the one-dimensional magnetic nano-chain is coated by adopting an inorganic substance or a polymer to obtain the permanently fixed one-dimensional magnetic nano-chain. Patent CN108711480A discloses a preparation method of magnetic mesoporous silica nanochain. However, the diameter of the one-dimensional magnetic nanochain is large, and the length is difficult to be precisely controlled.
The surface of the one-dimensional chain magnetic nano assembly is an oxide or a polymer capable of adsorbing a metal precursor, so that the functional magnetic nano stirrer catalyst can be prepared. Wang et al (RSC adv.,2016,6,97882-97889.) successfully prepared Fe by polymer encapsulation 3 O 4 The @ P (MAA-DVB) -Pd nano-chain catalyst can catalyze and reduce rhodamine B. Zhang et al (J.Colloid.Interf.Sci.,2015,456,145-154.) prepare one-dimensional Fe by precipitation polymerization 3 O 4 @ P (MBAAm-co-MAA) @ Ag nano chain, can effectively degrade 4-nitrophenol pollutants. Patent CN109935430A discloses a Fe 3 O 4 @SiO 2 @ C/Ni can be used as a catalyst for the degradation of aromatic nitro dyes. However, the one-dimensional nano-chain catalyst prepared by the method has the disadvantages of non-uniform size, large diameter and complex preparation process.
How to simply obtain the one-dimensional magnetic nano catalytic material so as to optimize the performance of the material to the maximum extent is still a difficult point to be solved.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of a noble metal-loaded magnetic nano stirrer catalyst, which comprises the following steps:
(1) uniformly mixing the magnetic nano stirrer and the noble metal solution to obtain a noble metal precursor;
(2) and (2) adding a reducing agent solution into the noble metal precursor solution obtained in the step (1), and preparing the noble metal-loaded magnetic nano stirrer catalyst by deposition reduction.
The magnetic nano stirrer is a self-made magnetic nano stirrer. The specific method refers to a preparation method of a magnetic nano stirrer (publication number CN 107138093A): homogeneously mixed FeCl 3 Heating and reacting with sodium oleate to obtain iron oleate; dissolving iron oleate in the mixed solution of oleic acid and 1-octadecene, heating and reacting to obtain oil-soluble Fe 3 O 4 A nanoparticle; obtaining water-soluble Fe by citric acid ligand exchange 3 O 4 Nano particles which are centrifugally dispersed in deionized water; mixing Fe 3 O 4 Mixing the nano particles, tetraethoxysilane and ammonia water, reacting under the action of a magnetic field, washing and separating to obtain the magnetic nano stirrer.
Further, in the step (2), the noble metal solution is HAuCl 4 、AgNO 3 、H 2 PdCl 4 And K 2 PtCl 6 At least one of (1).
Further, the catalyst loading in step (2) is 0.5 wt% to 5 wt%.
Further, the reducing agent in the step (2) is NaBH 4 、KBH 4 And ascorbic acid.
It is yet another object of the present invention to provide a noble metal-supported magnetic nanoscaler catalyst.
Further, the invention also provides application of the noble metal-loaded magnetic nano stirrer catalyst, and explores the catalytic rule of the noble metal-loaded magnetic nano stirrer catalyst on p-nitrophenol model reaction. The catalytic performance testing procedure was as follows: preparing p-nitrophenol (4-NP) and NaBH 4 Mixing the aqueous solutions, adding a certain amount of catalyst into the above mixed solution, and periodically sampling and passing through purpleThe exo-visible spectrophotometer monitored the change in concentration of 4-NP in solution.
Compared with the prior art, the invention has the following advantages:
the oxide layer on the surface of the magnetic nano stirrer can be used for conveniently adsorbing a metal precursor, and the noble metal-loaded magnetic nano stirrer catalyst with adjustable components and content is obtained through reduction treatment. The catalyst is used for a micro reaction system, so that the reaction is more flexible and diversified, and the design diversity and functionality of the micro catalytic reaction system are greatly improved. Due to the adoption of the technical scheme, compared with the prior art, the catalyst has the advantages of simple preparation process, good dispersibility, cheap and easily-obtained raw materials, low cost, good catalytic performance and the like.
Drawings
FIG. 1 is an SEM image of a magnetic nanoscrer of the present invention.
FIG. 2 is an SEM image of the Ag-loaded magnetic nano-stirring bar in example 2 of the present invention.
FIG. 3 is an SEM image of Pd-loaded magnetic nano-stirrer in example 3 of the present invention.
FIG. 4 is a UV-Vis reaction curve of the magnetic nano-stirring carrier for 4-NP in comparative example 1 of the present invention.
FIG. 5 is a UV-Vis reaction curve of Pd-loaded magnetic nano-stirrer on 4-NP in example 3 of the present invention.
Detailed Description
It is to be understood that within the scope of the present invention, the various features of the invention described above, as well as those described in the specific embodiments below, may be combined with each other to form new or preferred embodiments. For reasons of space, they will not be described in detail.
In order to better explain the invention, the preparation and application of the noble metal supported magnetic nano-stirrer catalyst are further explained in the following by combining the specific examples and the attached drawings.
Example 1
(1) 3mg of a home-made magnetic nano-stirrer was dispersed in 5mL of water, and 3. mu.L of 50mM HAuCl was added 4 The solution was stirred and immersed for 1h, 3mL of 1.25mg/mL KBH was added 4 Reducing the water solution for 0.5h, washing with water for three times, and separating by magnetic adsorption.
The preparation method of the magnetic nano stirrer comprises the following steps: taking 200 mu L of synthesized Fe 3 O 4 Adding the nano-particle solution into 1.4mL of mixed solution of water and isopropanol, adding 20 mu L of ethyl orthosilicate, uniformly mixing, and adding 30 mu L of ammonia water. Then assembling under the induction of a magnetic field, and dispersing in ethanol after washing. FIG. 1 is an SEM image of the prepared magnetic nano-stirring bar. It can be seen from the figure that under the condition of an external magnetic field, Fe 3 O 4 The nano particles are assembled into a micron chain structure along the direction of magnetic force lines, and the length is about 15-50 mu m.
(2) And (3) testing the catalytic performance: 0.5mM of p-nitrophenol and 0.5M of NaBH are added 4 Mixing the aqueous solutions, adding a catalyst into the mixed solution, and performing ultraviolet scanning at intervals. FIG. 4 is a UV-Vis reaction curve of magnetic stirring nanosupports on 4-NP, with hardly any catalytic effect.
Comparative example 1
3mg of a self-made magnetic nano stirrer is dispersed in 5mL of water, and the magnetic nano stirrer is directly used for catalytic test of p-nitrophenol without adding a metal precursor. The catalytic performance test was the same as the evaluation in example 1.
FIG. 4 is a graph showing the UV-Vis reaction curve of magnetic stirring nanosupports with 4-NP, and little reaction occurred.
Example 2
(1) 3mg of self-made nano stirring bar is dispersed in 5mL of water, and 8.87 mu L of AgNO with the concentration of 8mM is added 3 After the solution was stirred and immersed for 1 hour, 3mL of NaBH with a concentration of 1.25mg/mL was added 4 Reducing the water solution for 0.5h, washing with water for three times, and separating by magnetic adsorption. Among them, the method for preparing the magnetic nano-stirring bar was the same as that of embodiment example 1. FIG. 2 is an SEM image of the magnetic stirring nanospheres loaded with Ag in the example of the present invention, from which it can be seen that silver particles were successfully loaded on the magnetic stirring nanospheres.
(2) The catalytic performance test was the same as the evaluation in example 1.
Example 3
(1) Taking 3mg fromThe prepared nano-stirring bar was dispersed in 5mL of water, and 3. mu.L of 20mM H was added 2 PdCl 4 The solution was stirred and immersed for 1h, 3mL of NaBH at a concentration of 1.25mg/mL was added 4 Reducing the solution for 0.5h, washing with water for three times, and separating by magnetic adsorption. Among them, the method for preparing the magnetic nano-stirring bar was the same as that of embodiment example 1. FIG. 3 is an SEM image of a Pd-supported magnetic nano-stirrer in an example of the present invention, and it can be seen that palladium particles are successfully supported on the magnetic nano-stirrer.
(2) The catalytic performance test was the same as the evaluation test in example 1. FIG. 5 is a UV-Vis reaction curve of Pd-loaded magnetic nano-stirrer on 4-NP, and the conversion rate at 10min reaches 90%.
Example 4
(1) Dispersing 3mg of self-made nano stirring bar in 5mL of water, adding 3 mu L of K with the concentration of 10mM 2 PtCl 6 The solution was immersed under stirring for 1 hour, and then 3mL of an aqueous ascorbic acid solution having a concentration of 1.25mg/mL was added to reduce the solution for 0.5 hour, followed by washing with water three times and magnetic adsorption separation. Among them, the method for preparing the magnetic nano-stirring bar was the same as that of embodiment example 1.
(2) The catalytic performance test was the same as the evaluation in example 1.
The precious metal-loaded magnetic nano stirrer provided by the invention has a one-dimensional chain structure, the size, the structure and the catalyst components of the precious metal-loaded magnetic nano stirrer are adjustable, and the precious metal-loaded magnetic nano stirrer can be prepared by the implementation example method. Through a p-nitrophenol catalytic experiment, the catalyst is used for a micro reaction system, shows excellent catalytic effect, has paramagnetism and can be magnetically separated and recovered.
The foregoing is a teaching of preferred embodiments of the present invention only to assist in understanding the method of the present invention and its core ideas. It should be noted that the technical scope of the present invention for the technical field is not limited to the contents of the above-described embodiments, and other changes, modifications, substitutions, combinations, and so on based on the principle of the present invention are determined by the technical scope of the claims.
Claims (1)
1. Noble metal-loaded magnetic nanoparticle catalystCharacterized in that it is used in p-nitrophenol and NaBH 4 Adding a magnetic nano stirrer catalyst loaded with noble metal Pd into the aqueous solution mixture, and researching the catalytic performance of the mixture by reducing p-nitrophenol: 0.5mM of p-nitrophenol and 0.5M of NaBH are added 4 Mixing aqueous solutions, adding a magnetic nano stirrer catalyst loaded with noble metal Pd into the mixed solution, and performing ultraviolet scanning at intervals;
the preparation process of the magnetic nano stirrer catalyst loaded with noble metal Pd is as follows: dispersing 3mg of self-made nano stirring bar in 5mL of water, adding 3 mu L of H with the concentration of 20mM 2 PdCl 4 The solution was stirred and immersed for 1h, 3mL of NaBH at a concentration of 1.25mg/mL was added 4 Reducing the aqueous solution for 0.5h, washing with water for three times, and carrying out magnetic adsorption separation to obtain a magnetic nano stirrer catalyst loaded with noble metal Pd;
the preparation method of the magnetic nano stirrer comprises the following steps: taking 200 mu L of synthesized Fe 3 O 4 Adding the nano-particle solution into a mixed solution of 1.4mL of water and isopropanol, adding 20 mu L of ethyl orthosilicate, uniformly mixing, adding 30 mu L of ammonia water, then assembling under the induction of a magnetic field, and dispersing in ethanol after washing; the shell of the magnetic nano stirrer is SiO 2 The average size of the particles is 1-100 μm.
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