CN109420773B - Preparation method of nano zero-valent iron-based bimetal/trimetal material - Google Patents
Preparation method of nano zero-valent iron-based bimetal/trimetal material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano zero-valent iron-based bimetal/trimetal material, which comprises the following steps: and simultaneously feeding the metal salt mixed solution and the reducing agent solution into a stainless steel wire mesh filler rotary packed bed for reaction, magnetically separating reaction products after the reaction is finished, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and performing vacuum drying to obtain the nano zero-valent iron-based bimetallic/trimetal material with the particle size of 10-20 nm. The preparation method can prepare the nano zero-valent iron-based bimetallic/trimetal material with the one-dimensional size of 10-20nm and uniform particle size distribution; the prepared nano zero-valent iron-based bimetal/trimetal material has controllable size, uniform particle size distribution and no agglomeration, and the preparation process is simple, low in cost and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of energy conservation and environmental protection, and particularly relates to a preparation method of a nano zero-valent iron-based bimetal/trimetal material.
Background
The nanometer zero-valent iron is zero-valent iron particles with the particle size of 1-100nm, can be used for removing pollutants such as organic chloride, inorganic anions, heavy metals, organic dyes, pesticides and the like in water, and is an environmental nanometer material widely researched at present. Compared with the traditional iron powder material, the nano zero-valent iron has better adsorption performance and reaction activity because the particle size is smaller and the specific surface area and the surface energy are larger.
However, the nano zero-valent iron has poor stability, is easily oxidized and corroded in soil and underground water to form a passivation layer, so that the surface activity of the nano zero-valent iron is poor, the pollutant remediation efficiency is reduced, and the application of the nano zero-valent iron in practice is limited. In recent years, researches show that the activity of nano zero-valent iron can be improved by introducing other metals such as Ni, Pb, Cu, Pt, Ag and the like on the basis of nano iron, the added second metal can slow down the oxidation condition of the surface of the nano iron so as to keep the reduction activity of the nano iron, and the loaded metal also has a certain catalytic action, so that the degradation rate can be greatly improved, and the generation of toxic byproducts can be inhibited or reduced.
The coprecipitation method is simple and easy to operate, has mild experimental condition requirements, and is the most ideal nano zero-valent iron-based gold disulfide at presentA preparation method of a metal/trimetal material. However, when the precipitation reaction is carried out in a normal gravity field, the particle size distribution of the prepared bimetallic/trimetallic particles is not uniform and the agglomeration is serious due to the nonuniform micro-mixing. The traditional chemical precipitation method uses a stirring kettle for reaction, and the characteristic time (t) of micro-mixing uniformity in a traditional chemical reactorm) The characteristic time (tau) of the induced nucleation is longer than that of the induced nucleation, so that the nucleation and the growth process are in a non-uniform environment on a molecular scale, and the prepared bimetal/trimetal particles have the advantages of large particle size, nonuniform distribution, easy agglomeration, long reaction time and no continuous preparation capability. In addition, the continuous large-scale preparation is difficult to realize in the traditional reactor, the repeatability is poor, the agglomeration of the nano particles is aggravated and the particle size distribution is uncontrollable after the preparation is amplified, so that the industrial practical value is not realized.
At present, researchers have utilized supergravity technology to prepare nanomaterials, for example, supergravity technology has been successfully applied to TiO2、ZnO、BaSO4、CaCO3、BaTiO3、SiO2、LiMnO2And the like in the industrial production of various nano materials. The supergravity technology has the advantages of short reaction time, small particle size of the formed nano particles, uniform particle size distribution, low preparation cost, easy industrial amplification production (4-20 times higher than that of the conventional method) and the like. However, at present, no people utilize the supergravity technology to prepare the nano zero-valent iron-based bimetal/trimetal material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a nano zero-valent iron-based bimetal/trimetal material; the method can prepare the nanometer zero-valent iron-based bimetal/trimetal material with the one-dimensional size of 10-20nm and uniform particle size distribution; the problems that the nanometer zero-valent iron-based bimetal/trimetal material prepared by the existing method is poor in size controllability, uneven in particle size distribution, serious in agglomeration and the like are solved, and the preparation method is simple in process, low in cost and capable of realizing large-scale production.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a nano zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) the preparation method of the metal salt mixed solution comprises the following steps: dissolving metal iron salt, metal M salt and a surfactant in an ethanol solution to prepare a metal salt mixed solution;
2) the preparation method of the reducing agent solution comprises the following steps: dissolving a reducing agent in an ethanol solution to prepare a reducing agent solution;
3) adding the metal salt mixed solution into a liquid storage tank A, adding a reducing agent solution into a liquid storage tank B, and introducing nitrogen into the liquid storage tanks A and B to respectively remove oxygen in the solutions; starting a heating device to preheat the metal salt mixed solution and the reducing agent solution, starting a peristaltic pump to simultaneously convey the two raw material solutions to a rotary packed bed liquid distributor, and impacting the raw material solutions in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface, so as to complete preliminary mixing and reaction, and introducing nitrogen gas all the time in the reaction process;
4) controlling the rotating speed of the rotating packed bed, enabling the reaction liquid after the impact to flow from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, further mixing and reacting in the filler layer, throwing reactants out of the outer shell at the outer edge of the filler, and collecting the reactants to a liquid outlet to flow out under the action of gravity;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products obtained by separation to be neutral by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the nano zero-valent iron-based bimetallic/trimetal material with the particle size of 10-20 nm.
As a further improvement of the technical scheme, the rotary packed bed is a stainless steel wire gauze packing rotary packed bed.
The applicant has surprisingly found that the use of various existing high gravity rotating beds, such as: the baffle plate filler rotary packed bed, the regular filler rotary packed bed, the polyethylene filler rotary packed bed and the like cannot achieve the aim of the invention and cannot achieve the beneficial effects required by the invention, and the stainless steel wire mesh filler rotary packed bed is required to be specially used.
As a further improvement of the technical scheme, in the step 1), the metal iron salt comprises one or more of sulfate, nitrate and hydrochloride; the metal M comprises one or two of Cu, Ag, Pd, Pt and Ni; the surfactant comprises one or more of polyvinylpyrrolidone (PVP), Cetyl Trimethyl Ammonium Bromide (CTAB), Sodium Dodecyl Sulfate (SDS), Sodium Dodecyl Benzene Sulfonate (SDBS), carboxymethyl cellulose (CMC), polyacrylic acid (PAA) polyethylene glycol (PEG) and hydroxypropyl methylcellulose (HPMC).
As a further improvement of the technical solution, in step 1), the metal M salt includes one or two of copper chloride, copper sulfate, copper nitrate, silver nitrate, palladium chloride, palladium sulfate, palladium nitrate, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, nickel chloride, nickel sulfate, and nickel nitrate.
As a further improvement of the technical scheme, in the step 1), the concentration of the cations in the metal salt mixed solution is 0.05-5.0 mol/L; the doping ratio of the metal M is 0-50 wt%; the dosage of the surfactant is 0-30 wt%; preferably, the concentration of the cation in the metal salt mixed solution is 0.1-2.5mol/L, the doping ratio of the metal M is 1-25 wt%, and the dosage of the surfactant is 1-20 wt%; more preferably, the concentration of the cation in the metal salt mixed solution is 0.5-1.5mol/L, the doping ratio of the metal M is 5-20 wt%, and the amount of the surfactant is 1-10 wt%.
As a further improvement of the technical proposal, in the step 1) and the step 2), the volume concentration of the ethanol solution is 20-50%.
As a further improvement of the technical solution, in the step 2), the concentration of the anion in the reducing agent solution is 0.1-5.0mol/L, or 0.1-2.5mol/L, or 0.1-2.0mol/L, or 0.1-1.5mol/L, or 0.1-1.0mol/L, or 0.5-3.0mol/L, or 0.5-2.5mol/L, or 0.5-2.0mol/L, or 0.5-1.5mol/L, or 0.5-1.0mol/L, or 1-3.0mol/L, or 1-2.5mol/L, or 1-2.0mol/L, or 1-1.5 mol/L.
As a further improvement of the technical scheme, the reaction temperature in the stainless steel wire gauze packing rotating packed bed is 10-60 ℃, preferably 20-50 ℃.
As a further improvement of the technical scheme, the molar ratio of the reducing agent to the metal iron salt is 2-6: 1; preferably, it is 3-5: 1.
As a further improvement of the technical scheme, the rotating speed of the stainless steel wire gauze packing rotating packed bed is controlled to be 100-200 rpm, 500-2000rpm, 500-1800rpm, 500-1600rpm, 500-1400rpm, 500-1200rpm, 500-1000rpm, 500-800rpm, 700-2000rpm, 700-1800rpm, 700-1600rpm, 700-1400rpm, 700-1200rpm, 700-1000rpm, 1000-2000rpm, 1000-1800rpm, 1000-1600rpm, 1000-1400rpm or 1000-1200 rpm.
The bimetal/trimetal material obtained by the invention is as follows: Fe/M1/M2(M ═ Cu, Ag, Pd, Pt, Ni) bimetallic/trimetallic materials.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the nanometer zero-valent iron-based bimetallic/trimetal material by virtue of the wire mesh filler rotary packed bed, and utilizes the filler rotating at high speed to violently shear and crush the fluid to generate a huge and rapidly updated phase interface, so that the micromixing and mass transfer processes are greatly enhanced, and the characteristic time of micromixing uniformity in the wire mesh filler rotary packed bed is 1-10 microseconds, which is far shorter than the induced nucleation characteristic time of the traditional liquid phase precipitation reaction. That is, with the aid of the wire mesh packing rotating packed bed adopted by the invention, the nano zero-valent iron-based bimetal/trimetal material reaches uniform supersaturation in the reactor before crystallization nucleation, so that nucleation and growth of the prepared nano zero-valent iron-based bimetal/trimetal material are both carried out under the condition of uniform supersaturation, an ideal uniform nucleation environment is met, the nucleation process is controlled, particles present narrow distribution, and the prepared nano material has small particle size and uniform particle size distribution. The invention applies the wire mesh filler rotary packed bed with strong micro mixing characteristics to the rapid chemical precipitation reaction, and the prepared nano zero-valent iron-based bimetal/trimetal material has the advantages of small particle size, uniform particle size distribution, simple preparation method, low preparation cost and continuous batch preparation, thereby having prominent industrial application prospect.
The method can prepare the nanometer zero-valent iron-based bimetal/trimetal material with the one-dimensional size of 10-20nm and uniform particle size distribution.
Drawings
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings
FIG. 1 is a diagram of an apparatus for a rotating packed bed of stainless steel wire gauze packing used in the present invention;
FIG. 2 is a TEM image of the Fe/Cu bimetallic nanoparticles obtained in example 1;
FIG. 3 is a TEM image of the Fe/Ni bimetallic nanoparticles obtained in example 5;
FIG. 4 is a TEM image of the Fe/Cu bimetallic nanoparticles obtained in example 6;
FIG. 5 is a TEM image of Fe/Ni bimetallic nanoparticles obtained in example 7;
FIG. 6 is the SEM-EDS mapping analysis result of the Fe/Cu bimetallic nanoparticles obtained in example 6;
FIG. 7 is the SEM-EDS mapping analysis result of the Fe/Ni bimetallic nanoparticles obtained in example 7;
fig. 8 is an XRD pattern of the nano-bimetal obtained in each example, wherein (a) is example 1; (b) example 5 was used; (c) example 6 was used; (d) example 7 was used;
FIG. 9 is a TEM image of the Fe/Cu bimetallic nanoparticles obtained in comparative example 1;
FIG. 10 is a TEM image of the Fe/Ni bimetallic nanoparticles obtained in comparative example 2;
FIG. 11 is a TEM image of the Fe/Cu bimetallic nanoparticles obtained in comparative example 3;
FIG. 12 is a TEM image of the Fe/Ni bimetallic nanoparticles obtained in comparative example 4. (ii) a
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) FeSO is put into ethanol solution4·7H2O、CuSO4·5H2Preparing a metal salt mixed solution with the cation concentration of 0.05mol/L by using 4% of theoretical mass Cu/Fe (w/w), and adding 10% of PVP (polyvinyl pyrrolidone) as a surfactant;
2) in ethanol solution, as Fe2+And
in a molar ratio of 1: 3 preparing a sodium borohydride solution;
3) adding a metal salt mixed solution and a sodium borohydride solution into liquid storage tanks A and B, introducing nitrogen to remove oxygen in the solutions, starting a heating device to preheat the reaction liquid to 30 ℃, starting a peristaltic pump to convey the two raw material liquids to a liquid distributor through a flowmeter, and impacting the two raw material liquids in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface, so as to complete primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 1500rpm, and the reaction temperature in the rotating packed bed is 30 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain Fe/Cu bimetallic particles.
FIG. 2 shows a TEM image of the Fe/Cu bimetallic nanoparticles synthesized in this example, and it can be seen in FIG. 2 that the product morphology is mainly spherical, the particle size is about 20nm, and the size is uniform.
Fig. 8(a) shows an X-ray diffraction pattern of the Fe/Cu bimetallic nanoparticles synthesized in this example, and it can be seen in fig. 8(a) that the XRD pattern of the prepared Fe/Cu bimetallic nanoparticles is substantially identical to that of the Fe/Cu bimetallic nanoparticles reported in the literature, and characteristic diffraction peaks appear at 43.3 ° and 44.67 °, respectively corresponding to the (111) crystal plane of copper and the (110) crystal plane of iron, but there is a hetero-peak of an oxidizing substance, indicating that the prepared Fe/Cu bimetallic material is partially oxidized.
Example 2
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, Fe (NO)3)3·9H2O、AgNO3Preparing a metal salt mixed solution with the cation concentration of 0.05mol/L according to the theoretical mass of Ag/Fe (w/w) ═ 6%, and adding 10% CMC as a surfactant;
2) in ethanol solution, as Fe3+And
in a molar ratio of 1: 4 preparing a potassium borohydride solution;
3) adding the metal salt mixed solution and a potassium borohydride solution into the liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 2000rpm, and the reaction temperature in the rotating packed bed is 35 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain Fe/Ag bimetallic particles.
Example 3
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, Fe2(SO4)3、Pd(NO3)2Preparing a metal salt mixed solution with the cation concentration of 0.05mol/L according to the theoretical mass Pd/Fe (w/w) ═ 6%, and adding 5% SDS as a surfactant;
2) in ethanol solution, as Fe3+And
in a molar ratio of 1: 4 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 1000rpm, and the reaction temperature in the rotating packed bed is 40 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain Fe/Pd bimetallic particles.
Example 4
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, FeCl3、H2PtCl6According to the theoretical mass Pt/Fe (w/w) ═ 8%, metal salt with cation concentration of 0.05mol/L is preparedMixing the solution, and adding 10% of SDBS as a surfactant;
2) in ethanol solution, as Fe3+And
in a molar ratio of 1: 4 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 500rpm, and the reaction temperature in the rotating packed bed is 40 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain the Fe/Pt bimetallic particles.
Example 5
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, FeSO4·7H2O、Ni(NO3)2·6H2Preparing a metal salt mixed solution with the cation concentration of 0.05mol/L by using 5% of theoretical mass of Ni/Fe (w/w), and adding 10% of HPMC as a surfactant;
2) in ethanol solution, as Fe2+And
in a molar ratio of 1: 3 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 1500rpm, and the reaction temperature in the rotating packed bed is 45 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain Fe/Ni bimetallic particles.
FIG. 3 shows a TEM image of the Fe/Ni bimetallic nanoparticles synthesized in this example, and it can be seen in FIG. 3 that the product is mainly spherical in morphology, about 20nm in particle size and uniform in size.
Fig. 8(b) shows an X-ray diffraction pattern of the Fe/Ni bimetallic nanoparticles synthesized in this example, and it can be seen in fig. 8(b) that the XRD pattern of the prepared Fe/Ni bimetallic nanoparticles is substantially identical to the XRD pattern of the Fe/Ni bimetallic nanoparticles reported in the literature, and characteristic diffraction peaks appear at 44.51 ° and 44.67 °, respectively corresponding to the (111) crystal plane of nickel and the (110) crystal plane of iron, but there is a hetero-peak of an oxidizing substance, indicating that the prepared Fe/Ni bimetallic material is partially oxidized.
Example 6
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, FeSO4·7H2O、CuSO4·5H2Preparing a metal salt mixed solution with the cation concentration of 0.05mol/L by using 10% of theoretical mass of Cu/Fe (w/w), and adding 5% of CTAB as a surfactant;
2) in ethanol solution, as Fe2+And
is 1: 3 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 1500rpm, and the reaction temperature in the rotating packed bed is 40 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain Fe/Cu bimetallic particles.
FIG. 4 shows a TEM image of the Fe/Cu bimetallic nanoparticles synthesized in this example, and it can be seen in FIG. 4 that the product morphology is mainly spherical, the particle size is about 20nm, and the size is uniform.
Fig. 8(c) shows an X-ray diffraction pattern of the Fe/Cu bimetallic nanoparticles synthesized in this example, and it can be seen in fig. 8(c) that the XRD pattern of the prepared Fe/Cu bimetallic nanoparticles is substantially identical to the XRD pattern of the Fe/Cu bimetallic nanoparticles reported in the literature, and characteristic diffraction peaks appear at 43.3 ° and 44.67 °, respectively corresponding to the (111) crystal plane of copper and the (110) crystal plane of iron, but there is a hetero-peak of an oxidizing substance, indicating that the prepared Fe/Cu bimetallic material is partially oxidized.
Fig. 6 shows SEM-EDS mapping analysis results of the Fe/Cu bimetal nanoparticles synthesized in this example, and the calculated mass fraction of Cu element is 12.95%, which is slightly higher than the theoretical mass fraction, while the mass fraction of O element is 16.94%, which also proves that the prepared Fe/Cu bimetal is partially oxidized.
Example 7
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, FeSO4·7H2O、Ni(NO3)2·6H2Preparing a metal salt mixed solution with the cation concentration of 0.05mol/L by using 10% of theoretical mass of Ni/Fe (w/w), and adding 10% of PVP (polyvinyl pyrrolidone) as a surfactant;
2) in ethanol solution, as Fe2+And
in a molar ratio of 1: 3 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 1500rpm, and the reaction temperature in the rotating packed bed is 30 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain Fe/Ni bimetallic particles.
FIG. 5 shows a TEM image of the Fe/Ni bimetallic nanoparticles synthesized in this example, and it can be seen in FIG. 5 that the product is mainly spherical in morphology, about 20nm in particle size and uniform in size.
Fig. 8(d) shows an X-ray diffraction pattern of the Fe/Ni bimetallic nanoparticles synthesized in this example, and it can be seen in fig. 8(d) that the XRD pattern of the prepared Fe/Ni bimetallic nanoparticles is substantially identical to that of the Fe/Ni bimetallic nanoparticles reported in the literature, and characteristic diffraction peaks appear at 44.51 ° and 44.67 °, respectively corresponding to the (111) crystal plane of nickel and the (110) crystal plane of iron, but there is a hetero-peak of an oxidizing substance, indicating that the prepared Fe/Ni bimetallic material is partially oxidized.
Fig. 7 shows SEM-EDS mapping analysis results of the Fe/Ni bimetal nanoparticles synthesized in this example, and the calculated mass fraction of Ni element is 13.29%, which is slightly higher than the theoretical mass fraction, while the mass fraction of O element is 22.10%, which also proves that the prepared Fe/Ni bimetal is partially oxidized.
Example 8
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, FeCl3·6H2O、Ni(NO3)2·6H2O、CuSO4·5H2Preparing a metal salt mixed solution with the cation concentration of 0.5mol/L by using the theoretical mass of Ni/Fe (w/w) ═ 10% and Cu/Fe (w/w) ═ 8%, and adding 15% of PEG as a surfactant;
2) in ethanol solution, as Fe2+And
in a molar ratio of 1: 4 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 30 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 2000rpm, and the reaction temperature in the rotating packed bed is 40 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain the Fe/Ni/Cu trimetal particles.
Example 9
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1) in ethanol solution, Fe (NO)3)3·9H2O、AgNO3、CuSO4·5H2Preparing a metal salt mixed solution with the cation concentration of 0.65mol/L by using the theoretical mass of 5% Ag/Fe (w/w) and 10% Cu/Fe (w/w), and adding 10% PAA as a surfactant;
2) in ethanol solution, as Fe2+And
in a molar ratio of 1: 3.5 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 35 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are converged to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 2500rpm, and the reaction temperature in the rotating packed bed is 45 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain the Fe/Ag/Cu trimetal particles.
Example 10
A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material comprises the following steps:
1)in ethanol solution, FeCl2·4H2O、Pd(NO3)2、H2PtCl6Preparing a metal salt mixed solution with a cation concentration of 0.5mol/L according to theoretical mass Pd/Fe (w/w) ═ 5% and Pt/Fe (w/w) ═ 10%, and adding 10% SDS as a surfactant;
2) in ethanol solution, as Fe2+And
in a molar ratio of 1: 3 preparing a sodium borohydride solution;
3) adding the metal salt mixed solution and the sodium borohydride solution into liquid storage tanks A and B, and introducing nitrogen to remove oxygen in the solution. The heating device was turned on to preheat the reaction solution to 35 ℃. Starting a peristaltic pump to convey two raw material liquids to a liquid distributor through a flowmeter at the same time, and impacting in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface so as to finish primary mixing and reaction;
4) the reaction liquid after the impact flows from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, and is further mixed and reacted in the filler layer, reactants are thrown out of the outer shell at the outer edge of the filler and are collected to a liquid outlet to flow out under the action of gravity, the rotating speed of the rotating packed bed is controlled at 2500rpm, and the reaction temperature in the rotating packed bed is 40 ℃;
5) and after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products to be neutral by using deionized water and absolute ethyl alcohol, and drying the reaction products in vacuum to obtain the Fe/Pd/Pt trimetal particles.
Comparative example 1
The embodiment 1 is repeated, except that in the step 3), the metal salt mixed solution and the reducing agent solution are introduced into a baffle filler rotating packed bed through a peristaltic pump, after the reaction is finished, the reaction product is separated by magnetic separation, the reaction product is repeatedly washed to be neutral by deionized water and absolute ethyl alcohol, and the Fe/Cu bimetallic particles are obtained by vacuum drying.
FIG. 9 shows a TEM image of the Fe/Cu bimetallic nanoparticles synthesized in the comparative example, in FIG. 9, it can be seen that the Fe/Cu bimetallic nanoparticles are seriously agglomerated, the spherical structure cannot be basically seen, the particle size is large, the distribution is wide, the particle size is between 30 and 90nm, and the average particle size is about 60 nm. The average grain diameter of Fe/Cu bimetallic nano-particles prepared by the wire mesh filler rotating packed bed in the example 1 is about 20nm, the size is uniform, and the effect is better than that of a baffle plate filler rotating packed bed.
Comparative example 2
The embodiment 5 is repeated, except that in the step 3), the metal salt mixed solution and the reducing agent solution are introduced into the structured packing rotary packed bed through a peristaltic pump, after the reaction is finished, the reaction product is separated by magnetic separation, the product is repeatedly washed to be neutral by deionized water and absolute ethyl alcohol, and the Fe/Ni bimetallic particles are obtained by vacuum drying.
Fig. 10 shows a TEM image of the Fe/Ni bimetal particle synthesized in this comparative example, and it can be seen in fig. 10 that the Fe/Ni bimetal nanoparticle is heavily agglomerated, the spherical particle is not obvious, and the particle size is large and the distribution is wide, and the average particle size is about 30 nm. The average grain diameter of Fe/Ni bimetallic nanoparticles prepared by the wire mesh packing rotating packed bed in the example 5 is about 20nm, the size is uniform, and the effect is better than that of a regular packing rotating packed bed.
Comparative example 3
The embodiment 6 is repeated, except that in the step 3), the metal salt mixed solution and the reducing agent solution are introduced into the foamed nickel filler rotary packed bed through a peristaltic pump, after the reaction is finished, the reaction product is separated by magnetic separation, the product is repeatedly washed to be neutral by deionized water and absolute ethyl alcohol, and the Fe/Cu bimetallic particles are obtained by vacuum drying.
Fig. 11 shows a TEM image of the Fe/Cu bimetallic particles synthesized in this comparative example, and it can be seen in fig. 11 that the Fe/Cu bimetallic nanoparticles are strongly agglomerated, the spherical particles are not significant, the average particle diameter is about 35nm, and the particle diameter distribution is not uniform. The average grain diameter of Fe/Cu bimetallic nano-particles prepared by the wire mesh packing rotating packed bed in the example 6 is about 20nm, the size is uniform, and the effect is better than that of a regular packing rotating packed bed.
Comparative example 4
The embodiment 7 is repeated, except that in the step 3), the metal salt mixed solution and the reducing agent solution are introduced into the polyethylene filler rotating packed bed through a peristaltic pump, after the reaction is finished, the reaction product is separated by magnetic separation, the reaction product is repeatedly washed to be neutral by deionized water and absolute ethyl alcohol, and the Fe/Ni bimetallic particles are obtained by vacuum drying.
Fig. 12 shows a TEM image of the Fe/Ni bimetal particle synthesized in this comparative example, and it can be seen in fig. 12 that the Fe/Ni bimetal nanoparticle is seriously agglomerated, the spherical particle is not obvious, the average particle diameter is about 45nm, and the particle diameter distribution is not uniform. The average grain diameter of Fe/Ni bimetallic nano-particles prepared by the wire mesh filler rotating packed bed in the example 7 is about 20nm, the size is uniform, and the effect is better than that of the polyethylene filler rotating packed bed.
Comparative example 5
Example 2 was repeated except that, in step 3), the reaction solution was preheated to 70 ℃, and the resulting particles were seriously agglomerated. Therefore, the reaction temperature needs to be controlled within the preferable range, the products prepared by the method beyond the preferable range have certain agglomeration, and the application performance of the products is obviously reduced.
Comparative example 6
Example 3 is repeated, with the only difference that, in step 2), the process is carried out in accordance with Fe3+And
in a molar ratio of 1: 2 preparing a metal salt mixed solution and a sodium borohydride solution, wherein the obtained particles have uneven particle size distribution and larger particle size. It can be seen that the invention needs to control the molar ratio of the reactants within the preferred range, and the products produced by the method beyond the preferred range have a certain degree of agglomeration, and the application performance of the products is obviously reduced.
Comparative example 7
Example 4 was repeated except that in step 4), the rotation speed of the rotating packed bed was controlled to 200rpm, and the resulting particles had poor crystallinity and were highly susceptible to oxidation. As seen from the particles, the rotating speed of the rotating packed bed needs to be controlled within the preferable range, and the product prepared by the method beyond the preferable range has poor crystallinity and certain degree of agglomeration, so that the application performance of the product is obviously reduced.
In summary, in the present application, it is required to use the stainless steel wire gauze packing material as the rotating packed bed, and to match with the conditions of the specific reaction temperature, the specific molar ratio of the reducing agent to the metal iron salt, the specific rotating speed of the rotating packed bed, etc., and these technical characteristics are matched with each other to form an overall technical scheme, so as to obtain the nano zero-valent iron-based bimetallic/trimetallic material with a one-dimensional size of 10-20nm and uniform particle size distribution, thereby achieving the purpose of the present invention.
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. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (11)
1. A preparation method of a nanometer zero-valent iron-based bimetal/trimetal material is characterized by comprising the following steps:
1) dissolving metal iron salt, metal M salt and a surfactant in an ethanol solution to prepare a metal salt mixed solution;
2) dissolving a reducing agent in an ethanol solution to prepare a reducing agent solution;
3) adding the metal salt mixed solution into a liquid storage tank A, adding a reducing agent solution into a liquid storage tank B, and respectively introducing nitrogen into the liquid storage tank A and the liquid storage tank B to remove oxygen in the solution; starting a heating device to preheat the metal salt mixed solution and the reducing agent solution, starting a peristaltic pump to simultaneously convey the two raw material solutions to a rotary packed bed liquid distributor, and impacting the raw material solutions in opposite directions at a nozzle of the distributor to form an impact area with a fan-shaped fog surface, so as to complete preliminary mixing and reaction, and introducing nitrogen gas all the time in the reaction process;
4) controlling the rotating speed of the rotating packed bed, enabling the reaction liquid after the impact to flow from the inner edge to the outer edge of the packed bed along the filler pores under the action of centrifugal force, further mixing and reacting in the filler layer, throwing reactants out of the outer shell at the outer edge of the filler, and collecting the reactants to a liquid outlet to flow out under the action of gravity;
5) after the reaction is finished, magnetically separating reaction products, repeatedly cleaning the reaction products obtained by separation to be neutral by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a nano zero-valent iron-based bimetallic/trimetal material with the particle size of 10-20 nm;
the rotary packed bed is a stainless steel wire gauze packing rotary packed bed;
the reaction temperature in the stainless steel wire mesh filler rotary packed bed is 10-60 ℃;
the molar ratio of the reducing agent to the metal iron salt is 2-6: 1.
2. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: in the step 1), the metal iron salt comprises one or more of sulfate, nitrate and hydrochloride; the metal M comprises one or two of Cu, Ag, Pd, Pt and Ni; the surfactant comprises one or more of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol and hydroxypropyl methylcellulose.
3. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: in the step 1), the metal M salt comprises one or two of copper chloride, copper sulfate, copper nitrate, silver nitrate, palladium chloride, palladium sulfate, palladium nitrate, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, nickel chloride, nickel sulfate and nickel nitrate.
4. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1 or 2, wherein the method comprises the following steps: in the step 1), the concentration of cations in the metal salt mixed solution is 0.05-5.0 mol/L; the doping ratio of the metal M is 0-50 wt%; the amount of the surfactant is 0-30 wt%.
5. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 4, wherein the method comprises the following steps: the concentration of the cation in the metal salt mixed solution is 0.1-2.5mol/L, the doping ratio of the metal M is 1-25 wt%, and the dosage of the surfactant is 1-20 wt%.
6. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 5, wherein the method comprises the following steps: the concentration of the cation in the metal salt mixed solution is 0.5-1.5mol/L, the doping ratio of the metal M is 5-20 wt%, and the dosage of the surfactant is 1-10 wt%.
7. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: in the step 1) and the step 2), the volume concentration of the ethanol solution is 20-50%.
8. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: in the step 2), the reducing agent comprises one or more of sodium borohydride, potassium borohydride, hydrazine hydrate, tetrabutylammonium borohydride, sodium citrate, sodium hypophosphite, sodium phosphite and potassium tartrate;
the concentration of anions in the reducing agent solution is 0.1-5.0 mol/L.
9. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: the reaction temperature in the stainless steel wire gauze packing rotary packed bed is 20-50 ℃.
10. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: the molar ratio of the reducing agent to the metal iron salt is 3-5: 1.
11. The method for preparing nano zero-valent iron-based bimetal/trimetallic material according to claim 1, wherein the method comprises the following steps: the rotating speed of the stainless steel wire gauze packing rotating packed bed is controlled to be 500-2000 rpm.
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