CN109420773A - A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials - Google Patents
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials Download PDFInfo
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- CN109420773A CN109420773A CN201710743407.7A CN201710743407A CN109420773A CN 109420773 A CN109420773 A CN 109420773A CN 201710743407 A CN201710743407 A CN 201710743407A CN 109420773 A CN109420773 A CN 109420773A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- 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 kind of nano zero valence iron bimetallic/tri- metal materials preparation methods, steps are as follows: metal mixed salt solution and reducing agent solution being sent into stainless steel cloth filler rotary packed bed simultaneously and reacted, magnetic separation separates reaction product after reaction, it is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum drying obtains grain diameter in nano zero valence iron bimetallic/tri- metal materials of 10-20nm.Preparation method of the present invention can be made one-dimensional having a size of 10-20nm, the uniform nano zero valence iron bimetallic of particle diameter distribution/tri- metal materials；Prepared nano zero valence iron bimetallic/tri- metal material sizes are controllable, and particle diameter distribution is not reunited uniformly, and preparation process it is simple, it is low in cost, be produced on a large scale.
Description
Technical field
The invention belongs to energy conservation and environmental protection technology Material Fields, more particularly, to a kind of nano zero valence iron bimetallic/tri-
The preparation method of metal material.
Background technique
Nano zero valence iron is zero-valent iron particle of the partial size between 1-100nm, can be used for removing the organic chloride in water body
The pollutants such as object, inorganic anion, heavy metal, organic dyestuff and pesticide are the environment nano materials studied extensively at present.Because of it
Partial size is smaller, and specific surface area and surface can be larger, and compared with traditional iron powder materials, nano zero valence iron has better absorption property
And reactivity.
But nano zero-valence iron stability is poor, is easily oxidized in soil and groundwater and corrosion occurs and form passivation layer and make it
Surface-active is deteriorated, and reduces the remediation efficiency to pollutant, limits its application in practice.Research discovery in recent years
Other metals such as Ni, Pb, Cu, Pt, Ag etc. are introduced on the basis of Nanoscale Iron can be improved the activity of nano zero valence iron, addition
Second of metal, which can slow down the ironing surface oxidization condition of nanometer, makes it keep reduction activation, and in addition carried metal also has certain
Catalytic action can greatly improve degradation rate, and can inhibit or reduce the generation of harmful by-products.
For coprecipitation since operation is simple for it, experiment condition requirement is milder, has become at present ideal
Nano zero valence iron bimetallic/tri- metal materials preparation method.But when carrying out precipitation reaction in normal gravitational field, due to microcosmic
Mixing unevenly causes bimetallic/tri- metallic particles particle diameter distribution of preparation uneven and reunites more serious.Traditional chemical is heavy
Shallow lake method is reacted using stirred tank, the microcosmic uniformly mixed characteristic time (t in traditional chemical reactorm) it is greater than induction
The characteristic time (τ) of nucleation causes nucleation and growth course to be in the inhomogeneities environment on molecular scale, prepared double gold
/ tri- metallic particles partial sizes of category are big, are unevenly distributed, are easy to reunite, and the reaction time is long, and does not have the ability continuously prepared.In addition,
Continuous large scale preparation is difficult to realize in traditional reactor, repeatability is very poor after amplification preparation, nanoparticle agglomerates are aggravated, partial size
It is distributed uncontrollable, therefore does not have industrialization practical value.
Currently, having there is researcher to prepare nano material using high-gravity technology, for example, high-gravity technology is successfully answered
For TiO2、ZnO、BaSO4、CaCO3、BaTiO3、SiO2、LiMnO2Among industrialized production etc. a variety of nano materials.It is overweight
The nano particle diameter that power technology is short with the reaction time, is formed is small, particle diameter distribution is uniform, preparation cost is low, is easy to industrialize
The advantages that amplification production (4-20 times can be improved compared with conventional method).But currently, people utilizes high-gravity technology system not yet
Standby nano zero valence iron bimetallic/tri- metal materials.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nano zero valence iron bimetallic/tri- metal materials preparation sides
Method；It can be made one-dimensional having a size of 10-20nm, the uniform nano zero valence iron bimetallic of particle diameter distribution/tri- metals by this method
Material；Solve, grain poor using nano zero valence iron bimetallic/tri- metal material dimensional controllabilities prepared by existing method
Diameter is unevenly distributed and reunites the problems such as more serious, and the preparation method simple process, it is low in cost, be produced on a large scale.
In order to solve the above technical problems, invention adopts the following technical scheme that:
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, steps are as follows:
1) it is molten that etal molysite, metal M salt and surfactant the preparation method of metal mixed salt solution: are dissolved in ethyl alcohol
Metal mixed salt solution is configured in liquid；
2) preparation method of reducing agent solution: reducing agent is dissolved in ethanol solution and is configured to reducing agent solution；
3) metal mixed salt solution is added in A fluid reservoir, reducing agent solution is added in B fluid reservoir, A fluid reservoir
Nitrogen, which is passed through, with B fluid reservoir removes oxygen in solution respectively；Open heating device preheated metallic mixed salt solution and reducing agent
Two kinds of material liquids are delivered to rotary packed bed liquid distribution trough simultaneously by solution, starting peristaltic pump, and at the nozzle of distributor
It is opposite to hit the impingement region for forming fan-shaped cloudy surface, preliminary mixing, reaction are completed, is passed through nitrogen always in reaction process；
4) control rotary packed bed revolving speed, the reaction solution after shock under the influence of centrifugal force, along filler hole by filler
The inner edge of bed is flowed to outer rim, and the further hybrid reaction in packing layer, reactant are thrown away on shell at filler outer rim,
It is pooled to liquid outlet outflow under gravity；
5) after reaction, magnetic separation separates reaction product, separates the reaction product deionized water and dehydrated alcohol of acquisition
It is cleaned repeatedly to neutrality, vacuum drying obtains grain diameter in nano zero valence iron bimetallic/tri- metal materials of 10-20nm.
As the further improvement of technical solution, the rotary packed bed is stainless steel cloth filler rotary packed bed.
Applicant is found surprisingly that, using existing various high-gravity rotating bed, such as: baffle filler rotary packed bed,
Structured packing rotary packed bed, polyethylene carrier rotary packed bed etc. can not reach goal of the invention of the invention, can not reach
To the present invention claims beneficial effect, the present invention need it is specific use stainless steel cloth filler rotary packed bed.
As the further improvement of technical solution, in step 1), the etal molysite includes sulfate, nitrate, hydrochloric acid
One of salt is a variety of；Metal M includes one or both of Cu, Ag, Pd, Pt, Ni；The surfactant includes poly- second
Alkene pyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), lauryl sodium sulfate (SDS), dodecyl benzene sulfonic acid
Sodium (SDBS), carboxymethyl cellulose (CMC), polyacrylic acid (PAA) polyethylene glycol (PEG), in hydroxypropyl methylcellulose (HPMC)
It is one or more.
As the further improvement of technical solution, in step 1), the metal M salt includes copper chloride, copper sulphate, nitric acid
Copper, silver nitrate, palladium chloride, palladium sulfate, palladium nitrate, chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate, nickel chloride, nickel sulfate, nickel nitrate
One or both of.
As the further improvement of technical solution, in step 1), in step 1), metal mixed salt solution middle-jiao yang, function of the spleen and stomach ion concentration
For 0.05-5.0mol/L；The doping of metal M is compared for 0-50wt%；The dosage of surfactant is 0-30wt%；Preferably, golden
Belonging to cation concn in mixed salt solution is 0.1-2.5mol/L, and the doping of metal M is compared for 1-25wt%, the use of surfactant
Amount is 1-20wt%；It is highly preferred that metal mixed salt solution middle-jiao yang, function of the spleen and stomach ion concentration is 0.5-1.5mol/L, the doping ratio of metal M
For 5-20wt%, the dosage of surfactant is 1-10wt%.
As the further improvement of technical solution, in step 1) and step 2), the volumetric concentration of ethanol solution is 20-
50%.
As the further improvement of technical solution, in step 2), anion concentration is 0.1-5.0mol/ in reducing agent solution
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 1-1.5mol/L.
As the further improvement of technical solution, the reaction temperature in the stainless steel cloth filler rotary packed bed is
10-60 DEG C, it is preferable that reaction temperature is 20-50 DEG C.
As the further improvement of technical solution, the molar ratio of the reducing agent and etal molysite is 2-6:1；Preferably,
For 3-5:1.
As the further improvement of technical solution, control stainless steel cloth filler rotary packed bed revolving speed is 100-
2800rpm or 500-2000rpm or 500-1800rpm or 500-1600rpm or 500-1400rpm or 500-
1200rpm or 500-1000rpm or 500-800rpm or 700-2000rpm or 700-1800rpm or 700-1600rpm,
Or 700-1400rpm or 700-1200rpm or 700-1000rpm or 1000-2000rpm or 1000-1800rpm, or
1000-1600rpm or 1000-1400rpm or 1000-1200rpm.
The bimetallic that the present invention obtains/tri- metal materials are as follows: Fe/M1/M2(M=Cu, Ag, Pd, Pt, Ni) bimetallic/tri- gold medals
Belong to material.
Any range documented by the present invention includes any numerical value between end value and end value and end value or end value
Between any subrange for being constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in fields can be used or carried out referring to the prior art of fields.
Compared with prior art, the invention has the following beneficial effects:
The present invention prepares nano zero valence iron bimetallic/tri- metal materials by wire packing rotary packed bed, utilizes height
The filler of speed rotation is acutely sheared and is crushed to fluid, phase interface that is huge and quickly updating is generated, so that microcosmic mixing
Great reinforcing is obtained with mass transport process, the microcosmic uniformly mixed characteristic time is that 1-10 is micro- in wire packing rotary packed bed
Second, much smaller than the induction Nucleation characteristics time of Traditional liquid phase precipitation reaction.That is, being filled out by silk screen of the present invention
Expect rotary packed bed, nano zero valence iron bimetallic/tri- metal materials have reached uniformly before crystallization nucleation, in reactor
Degree of supersaturation, therefore prepared nano zero valence iron bimetallic/tri- metal materials nucleation and growth are uniform at one
It is carried out under conditions of degree of supersaturation, meets desired homogeneous into nuclear environment, control nucleation process, particle is made to show relatively narrow point
Cloth, the partial size of prepared nano material is smaller, particle diameter distribution is uniform.The present invention is by the silk screen with powerful microcosmic composite character
Filler rotary packed bed is reacted applied to quick chemical precipitation, nano zero valence iron bimetallic/tri- metal materials tool of preparation
Have partial size is small, particle diameter distribution is uniform, preparation method is simple, preparation cost is low, can continuous batch preparation, therefore have work outstanding
Industry application prospect.
Method of the invention can be made one-dimensional having a size of 10-20nm, and the uniform nano zero valence iron bimetallic of particle diameter distribution/
Three metal materials.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing
Fig. 1 is the device figure for the stainless steel cloth filler rotary packed bed that the present invention uses；
Fig. 2 is that the TEM of the obtained Fe/Cu duplex metal nano granule of embodiment 1 schemes；
Fig. 3 is that the TEM of the obtained Fe/Ni duplex metal nano granule of embodiment 5 schemes；
Fig. 4 is that the TEM of the obtained Fe/Cu duplex metal nano granule of embodiment 6 schemes；
Fig. 5 is that the TEM of the obtained Fe/Ni duplex metal nano granule of embodiment 7 schemes；
Fig. 6 is that the SEM-EDS mapping of the obtained Fe/Cu duplex metal nano granule of embodiment 6 analyzes result；
Fig. 7 is that the SEM-EDS mapping of the obtained Fe/Ni duplex metal nano granule of embodiment 7 analyzes result；
Fig. 8 is the XRD diagram of bimetallic nano material obtained in each embodiment, and (a) is embodiment 1 in figure；(b) it is
Embodiment 5；It (c) is embodiment 6；It (d) is embodiment 7；
Fig. 9 is that the TEM of the obtained Fe/Cu duplex metal nano granule of comparative example 1 schemes；
Figure 10 is that the TEM of the obtained Fe/Ni duplex metal nano granule of comparative example 2 schemes；
Figure 11 is that the TEM of the obtained Fe/Cu duplex metal nano granule of comparative example 3 schemes；
Figure 12 is that the TEM of the obtained Fe/Ni duplex metal nano granule of comparative example 4 schemes.；
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Embodiment 1
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) by FeSO in ethanol solution4·7H2O、CuSO4·5H2O is prepared according to Theoretical Mass Cu/Fe (w/w)=4%
The metal mixed salt solution for being 0.05mol/L at cation concn adds 10%PVP as surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:3 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen, open heating device for reaction solution and be preheating to 30 DEG C, starting peristaltic pump is defeated through flowmeter simultaneously by two kinds of material liquids
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 1500rpm, rotary packed bed is 30 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Cu bimetal granule.
Fig. 2 shows the TEM of the Fe/Cu duplex metal nano granule of embodiment synthesis to scheme, visible product pattern master in Fig. 2
It to be spherical shape, partial size about 20nm is uniform in size.
Fig. 8 (a) shows the X-ray diffractogram of the Fe/Cu duplex metal nano granule of embodiment synthesis, can in Fig. 8 (a)
See the XRD spectrum of the Fe/Cu bimetal nano particles prepared by it and the XRD of Fe/Cu duplex metal nano granule reported in the literature
Map is almost the same, characteristic diffraction peak occurs in 43.3 ° and 44.67 °, respectively corresponds (111) crystal face of copper and (110) of iron
Crystal face, but there are the miscellaneous peak of oxidation material, illustrate that prepared Fe/Cu bimetal part is oxidized.
Embodiment 2
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by Fe (NO3)3·9H2O、AgNO3It is configured to according to Theoretical Mass Ag/Fe (w/w)=6%
Cation concn is the metal mixed salt solution of 0.05mol/L, adds 10%CMC as surfactant；
2) in ethanol solution, according to Fe3+WithMolar ratio be 1:4 be configured to solution of potassium borohydride；
3) metal mixed salt solution and solution of potassium borohydride are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 2000rpm, rotary packed bed is 35 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Ag bimetal granule.
Embodiment 3
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by Fe2(SO4)3、Pd(NO3)2Sun is configured to according to Theoretical Mass Pd/Fe (w/w)=6%
Ion concentration is the metal mixed salt solution of 0.05mol/L, adds 5%SDS as surfactant；
2) in ethanol solution, according to Fe3+WithMolar ratio be 1:4 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 1000rpm, rotary packed bed is 40 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Pd bimetal granule.
Embodiment 4
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by FeCl3、H2PtCl6Cation is configured to according to Theoretical Mass Pt/Fe (w/w)=8%
Concentration is the metal mixed salt solution of 0.05mol/L, adds 10%SDBS as surfactant；
2) in ethanol solution, according to Fe3+WithMolar ratio be 1:4 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 500rpm, rotary packed bed is 40 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Pt bimetal granule.
Embodiment 5
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by FeSO4·7H2O、Ni(NO3)2·6H2O is according to Theoretical Mass Ni/Fe (w/w)=5%
It is configured to the metal mixed salt solution that cation concn is 0.05mol/L, adds 10%HPMC as surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:3 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 1500rpm, rotary packed bed is 45 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Ni bimetal granule.
Fig. 3 shows the TEM figure of the Fe/Ni duplex metal nano granule of embodiment synthesis, visible product pattern master in Fig. 3
It to be spherical shape, partial size about 20nm is uniform in size.
Fig. 8 (b) shows the X-ray diffractogram of the Fe/Ni duplex metal nano granule of embodiment synthesis, can in Fig. 8 (b)
See the XRD spectrum of the Fe/Ni duplex metal nano granule prepared by it and the XRD of Fe/Ni duplex metal nano granule reported in the literature
Map is almost the same, characteristic diffraction peak occur in 44.51 ° and 44.67 °, respectively corresponds (111) crystal face and iron of nickel
(110) crystal face, but there are the miscellaneous peak of oxidation material, illustrate that prepared Fe/Ni bimetal part is oxidized.
Embodiment 6
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by FeSO4·7H2O、CuSO4·5H2O matches according to Theoretical Mass Cu/Fe (w/w)=10%
The metal mixed salt solution that cation concn is 0.05mol/L is made, adds 5%CTAB as surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:3 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 1500rpm, rotary packed bed is 40 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Cu bimetal granule.
Fig. 4 shows the TEM figure of the Fe/Cu duplex metal nano granule of embodiment synthesis, visible product pattern master in Fig. 4
It to be spherical shape, partial size about 20nm is uniform in size.
Fig. 8 (c) shows the X-ray diffractogram of the Fe/Cu duplex metal nano granule of embodiment synthesis, can in Fig. 8 (c)
See the XRD spectrum of the Fe/Cu duplex metal nano granule prepared by it and the XRD of Fe/Cu duplex metal nano granule reported in the literature
Map is almost the same, characteristic diffraction peak occurs in 43.3 ° and 44.67 °, respectively corresponds (111) crystal face of copper and (110) of iron
Crystal face, but there are the miscellaneous peak of oxidation material, illustrate that prepared Fe/Cu bimetal part is oxidized.
Fig. 6 show the embodiment synthesis Fe/Cu duplex metal nano granule SEM-EDS mapping analysis as a result,
The mass fraction that Cu element is calculated is 12.95%, slightly above Theoretical Mass score, while the mass fraction of O element is
16.94%, also confirmation illustrates that prepared Fe/Cu bimetal part is oxidized.
Embodiment 7
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by FeSO4·7H2O、Ni(NO3)2·6H2O is according to Theoretical Mass Ni/Fe (w/w)=10%
It is configured to the metal mixed salt solution that cation concn is 0.05mol/L, adds 10%PVP as surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:3 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 1500rpm, rotary packed bed is 30 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain Fe/Ni bimetal granule.
Fig. 5 shows the TEM figure of the Fe/Ni duplex metal nano granule of embodiment synthesis, visible product pattern master in Fig. 5
It to be spherical shape, partial size about 20nm is uniform in size.
Fig. 8 (d) shows the X-ray diffractogram of the Fe/Ni duplex metal nano granule of embodiment synthesis, can in Fig. 8 (d)
See the XRD spectrum of the Fe/Ni duplex metal nano granule prepared by it and the XRD of Fe/Ni bimetal nano particles reported in the literature
Map is almost the same, characteristic diffraction peak occur in 44.51 ° and 44.67 °, respectively corresponds (111) crystal face and iron of nickel
(110) crystal face, but there are the miscellaneous peak of oxidation material, illustrate that prepared Fe/Ni bimetal part is oxidized.
Fig. 7 show the embodiment synthesis Fe/Ni duplex metal nano granule SEM-EDS mapping analysis as a result,
The mass fraction that Ni element is calculated is 13.29%, slightly above Theoretical Mass score, while the mass fraction of O element is
22.10%, also confirmation illustrates that prepared Fe/Ni bimetal part is oxidized.
Embodiment 8
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by FeCl3·6H2O、Ni(NO3)2·6H2O、CuSO4·5H2O is according to Theoretical Mass Ni/
Fe (w/w)=10% and Cu/Fe (w/w)=8% is configured to the metal mixed salt solution that cation concn is 0.5mol/L, addition
15%PEG is as surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:4 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 30 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 2000rpm, rotary packed bed is 40 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain tri- metallic particles of Fe/Ni/Cu.
Embodiment 9
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by Fe (NO3)3·9H2O、AgNO3、CuSO4·5H2O is according to Theoretical Mass Ag/Fe (w/w)
=5% and Cu/Fe (w/w)=10% is configured to the metal mixed salt solution that cation concn is 0.65mol/L, addition 10%
PAA is as surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:3.5 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 35 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 2500rpm, rotary packed bed is 45 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain tri- metallic particles of Fe/Ag/Cu.
Embodiment 10
A kind of preparation method of nano zero valence iron bimetallic/tri- metal materials, includes the following steps:
1) in ethanol solution, by FeCl2·4H2O、Pd(NO3)2、H2PtCl6According to Theoretical Mass Pd/Fe (w/w)=
5% and Pt/Fe (w/w)=10% is configured to the metal mixed salt solution that cation concn is 0.5mol/L, and addition 10%SDS makees
For surfactant；
2) in ethanol solution, according to Fe2+WithMolar ratio be 1:3 be configured to sodium borohydride solution；
3) metal mixed salt solution and sodium borohydride solution are added in fluid reservoir A and B, and are passed through nitrogen and remove solution
In oxygen.It opens heating device and reaction solution is preheating to 35 DEG C.Start peristaltic pump two kinds of material liquids are defeated through flowmeter simultaneously
It send to liquid distribution trough, and shock forms the impingement region of fan-shaped cloudy surface in opposite directions at the nozzle of distributor, completion is preliminary to be mixed, is anti-
It answers；
4) reaction solution after hitting is flowed from the inner edge of packed bed to outer rim under the influence of centrifugal force, along filler hole,
And the further hybrid reaction in packing layer, reactant throw away on shell at filler outer rim, collect under gravity
It is flowed out to liquid outlet, controlling reaction temperature of the revolving speed of rotary packed bed in 2500rpm, rotary packed bed is 40 DEG C；
5) after reaction, magnetic separation separates reaction product, is cleaned repeatedly with deionized water and dehydrated alcohol to neutrality, vacuum
It is dried to obtain tri- metallic particles of Fe/Pd/Pt.
Comparative example 1
Embodiment 1 is repeated, the difference is that only, in step 3), metal mixed salt solution and reducing agent solution are passed through
Peristaltic pump is passed through in baffle filler rotary packed bed, and after reaction, magnetic separation separates reaction product, with deionized water and anhydrous second
Alcohol is cleaned repeatedly to neutrality, and vacuum drying obtains Fe/Cu bimetal granule.
Fig. 9 shows the TEM figure of the Fe/Cu duplex metal nano granule of comparative example synthesis, the visible bis- gold of Fe/Cu in Fig. 9
Metal nano-particle is reunited seriously, can't see due spherical structure substantially, and grain diameter is larger, wider distribution, partial size exists
Between 30-90nm, average grain diameter is about 60nm.The Fe/Cu bimetal nano that in embodiment 1 prepared by wire packing rotary packed bed
Mean particle size is about 20nm and uniform in size, and effect is better than baffle filler rotary packed bed.
Comparative example 2
Embodiment 5 is repeated, the difference is that only, in step 3), metal mixed salt solution and reducing agent solution are passed through
Peristaltic pump is passed through in structured packing rotary packed bed, and after reaction, magnetic separation separates reaction product, with deionized water and anhydrous second
Alcohol is cleaned repeatedly to neutrality, and vacuum drying obtains Fe/Ni bimetal granule.
Figure 10 shows the TEM figure of the Fe/Ni bimetal granule of comparative example synthesis, visible Fe/Ni bimetallic in Figure 10
Nanoparticle agglomerates are serious, and spheric granules is unobvious, and grain diameter is larger, wider distribution, and average grain diameter is about 30nm.Implement
The Fe/Ni duplex metal nano granule average grain diameter that in example 5 prepared by wire packing rotary packed bed is about 20nm and uniform in size, effect
Fruit is better than structured packing rotary packed bed.
Comparative example 3
Embodiment 6 is repeated, the difference is that only, in step 3), metal mixed salt solution and reducing agent solution are passed through
Peristaltic pump is passed through in nickel foam filler rotary packed bed, and after reaction, magnetic separation separates reaction product, with deionized water and anhydrous
Ethyl alcohol is cleaned repeatedly to neutrality, and vacuum drying obtains Fe/Cu bimetal granule.
Figure 11 shows the TEM figure of the Fe/Cu bimetal granule of comparative example synthesis, visible Fe/Cu bimetallic in Figure 11
Nanoparticle agglomerates are serious, and spheric granules is unobvious, and average grain diameter is about 35nm and particle diameter distribution is uneven.Silk in embodiment 6
The Fe/Cu duplex metal nano granule average grain diameter of net filler rotary packed bed preparation is about 20nm and uniform in size, and effect is better than
Structured packing rotary packed bed.
Comparative example 4
Embodiment 7 is repeated, the difference is that only, in step 3), metal mixed salt solution and reducing agent solution are passed through
Peristaltic pump is passed through in polyethylene carrier rotary packed bed, and after reaction, magnetic separation separates reaction product, with deionized water and anhydrous
Ethyl alcohol is cleaned repeatedly to neutrality, and vacuum drying obtains Fe/Ni bimetal granule.
Figure 12 shows the TEM figure of the Fe/Ni bimetal granule of comparative example synthesis, visible Fe/Ni bimetallic in Figure 12
Nanoparticle agglomerates are serious, and spheric granules is unobvious, and average grain diameter is about 45nm and particle diameter distribution is uneven.Silk in embodiment 7
The Fe/Ni duplex metal nano granule average grain diameter of net filler rotary packed bed preparation is about 20nm and uniform in size, and effect is better than
Polyethylene carrier rotary packed bed.
Comparative example 5
Embodiment 2 is repeated, the difference is that only, in step 3), reaction solution is preheating to 70 DEG C, gained particle generates
Serious agglomeration.It can thus be seen that the present invention need to control reaction temperature in the preferred scope, go beyond the scope institute
Product obtained has a degree of reunion, and application performance can be decreased obviously.
Comparative example 6
Embodiment 3 is repeated, the difference is that only, in step 2), according to Fe3+WithMolar ratio be 1:2 prepare
Metal mixed salt solution and sodium borohydride solution, gained particle size distribution is uneven and partial size is larger.It can thus be seen that this
Invention need to control reactant molar ratio in the preferred scope, and the obtained product that goes beyond the scope has a degree of group
Poly-, application performance can be decreased obviously.
Comparative example 7
Embodiment 4 is repeated, the difference is that only, in step 4), the revolving speed for controlling rotary packed bed is 200rpm, institute
It is poor to obtain grain crystalline degree, easily aoxidizes.Thus particle is found out, the present invention need to control rotary packed bed revolving speed described excellent
It selects in range, the obtained product crystallinity that goes beyond the scope is poor, and has a degree of reunion, under application performance meeting is obvious
Drop.
In conclusion in this application, not only needing specific use stainless steel cloth filler rotary packed bed, it is also necessary to match
Close the conditions such as the molar ratio of specific reaction temperature, reducing agent and etal molysite and the revolving speed of rotary packed bed, these technologies
Feature cooperates, and forming overall technical architecture can just be made one-dimensional having a size of 10-20nm, the uniform nanometer zero of particle diameter distribution
The iron-based bimetallic of valence/tri- metal materials, to reach goal of the invention of the invention.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of nano zero valence iron bimetallic/tri- metal materials preparation method, which is characterized in that steps are as follows:
1) etal molysite, metal M salt and surfactant are dissolved in ethanol solution and are configured to metal mixed salt solution；
2) reducing agent is dissolved in ethanol solution and is configured to reducing agent solution；
3) metal mixed salt solution is added in A fluid reservoir, reducing agent solution is added in B fluid reservoir, A fluid reservoir and B
Fluid reservoir each leads into the oxygen in nitrogen removing solution；It opens heating device preheated metallic mixed salt solution and reducing agent is molten
Two kinds of material liquids are delivered to rotary packed bed liquid distribution trough, and the phase at the nozzle of distributor by liquid, starting peristaltic pump simultaneously
To the impingement region for forming fan-shaped cloudy surface is hit, preliminary mixing, reaction are completed, is passed through nitrogen always in reaction process；
4) control rotary packed bed revolving speed, the reaction solution after shock under the influence of centrifugal force, along filler hole by packed bed
Inner edge is flowed to outer rim, and the further hybrid reaction in packing layer, reactant are thrown away on shell at filler outer rim, in weight
Liquid outlet outflow is pooled under the action of power；
5) after reaction, magnetic separation separates reaction product, and the reaction product deionized water for separating acquisition and dehydrated alcohol are repeatedly
Cleaning to neutrality, vacuum drying obtains grain diameter in nano zero valence iron bimetallic/tri- metal materials of 10-20nm.
2. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: institute
Stating rotary packed bed is stainless steel cloth filler rotary packed bed.
3. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: step
It is rapid 1) in, the etal molysite includes one of sulfate, nitrate, hydrochloride or a variety of；Metal M include Cu, Ag, Pd,
One or both of Pt, Ni；The surfactant includes polyvinylpyrrolidone, cetyl trimethylammonium bromide, ten
Sodium dialkyl sulfate, neopelex, carboxymethyl cellulose, polyacrylic acid, polyethylene glycol, in hydroxypropyl methylcellulose
It is one or more.
4. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: step
It is rapid 1) in, the metal M salt includes copper chloride, copper sulphate, copper nitrate, silver nitrate, palladium chloride, palladium sulfate, palladium nitrate, chlorine platinum
One or both of acid, platinic sodium chloride, potassium chloroplatinate, nickel chloride, nickel sulfate, nickel nitrate.
5. according to claim 1 or the 3 nano zero valence iron bimetallics/tri- metal materials preparation method, it is characterised in that:
In step 1), metal mixed salt solution middle-jiao yang, function of the spleen and stomach ion concentration is 0.05-5.0mol/L；The doping of metal M is compared for 0-50wt%；Table
The dosage of face activating agent is 0-30wt%；Preferably, metal mixed salt solution middle-jiao yang, function of the spleen and stomach ion concentration is 0.1-2.5mol/L, metal
The doping of M is compared for 1-25wt%, and the dosage of surfactant is 1-20wt%；It is highly preferred that metal mixed salt solution middle-jiao yang, function of the spleen and stomach from
Sub- concentration is 0.5-1.5mol/L, and the doping of metal M is compared for 5-20wt%, and the dosage of surfactant is 1-10wt%.
6. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: step
Rapid 1) and in step 2), the volumetric concentration of ethanol solution is 20-50%.
7. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: step
It is rapid 2) in, the reducing agent includes sodium borohydride, potassium borohydride, hydrazine hydrate, tetrabutyl ammonium borohydride, sodium citrate, secondary phosphorous
One of sour sodium, sodium phosphite, potassium tartrate are a variety of；
Anion concentration is 0.1-5.0mol/L or 0.1-2.5mol/L or 0.1-2.0mol/L or 0.1- in reducing agent solution
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 1-1.5mol/L.
8. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: institute
Stating the reaction temperature in stainless steel cloth filler rotary packed bed is 10-60 DEG C, it is preferable that reaction temperature is 20-50 DEG C.
9. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: institute
The molar ratio for stating reducing agent and etal molysite is 2-6:1；It preferably, is 3-5:1.
10. nano zero valence iron bimetallic/tri- metal materials preparation method according to claim 1, it is characterised in that: control
Stainless steel cloth filler rotary packed bed revolving speed processed is 100-2800rpm or 500-2000rpm or 500-1800rpm, or
500-1600rpm or 500-1400rpm or 500-1200rpm or 500-1000rpm or 500-800rpm or 700-
2000rpm or 700-1800rpm or 700-1600rpm or 700-1400rpm or 700-1200rpm or 700-
1000rpm or 1000-2000rpm or 1000-1800rpm or 1000-1600rpm or 1000-1400rpm or 1000-
1200rpm。
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