CN106904657A - FeOOH nano-particle of size adjustable and preparation method thereof - Google Patents
FeOOH nano-particle of size adjustable and preparation method thereof Download PDFInfo
- Publication number
- CN106904657A CN106904657A CN201710169820.7A CN201710169820A CN106904657A CN 106904657 A CN106904657 A CN 106904657A CN 201710169820 A CN201710169820 A CN 201710169820A CN 106904657 A CN106904657 A CN 106904657A
- Authority
- CN
- China
- Prior art keywords
- particle
- preparation
- nano
- feooh nano
- feooh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
FeOOH nano-particle the invention discloses a kind of size adjustable and preparation method thereof, by controlling the change of the pH value in reaction time and reaction system in the preparation method, and then obtain size different FeOOHs (FeOOH) nano-particle.The preparation method includes：First by molysite, be dissolved in obtained solution in solvent；Then in carboxylate, alkaline matter being added into the solution simultaneously；Again to addition urea in the solution with prepared mixed liquor；Finally the mixed liquor is heated, natural cooling is obtained the FeOOH nano-particle.
Description
Technical field
The present invention relates to field of inorganic nano material, in particular it relates to the FeOOH nano-particle of size adjustable and
Its preparation method.
Background technology
At present, FeOOH (FeOOH) nano-particle of most of synthesis is fusiformis, and its size is difficult to control to, and ratio
The nano-particle that surface area can not show a candle to ball is big.The preparation method of FeOOH nano materials mainly has iron chloride Hydrolyze method, protochloride
Iron air oxidation process and hydro-thermal Hydrolyze method, and assembled and hydro-thermal forced hydrolysis method collective effect by surfactant.And this
A little methods are beneficial to be grown to bar-shaped or fusiformis.The FeOOH that we synthesize, by numerous minimum particle gradually heap
Product is formed, and piles up glomeration, substantially increases its specific surface area.
And used as inorganic nano-particle, the application of the shape and specific surface area of its particle to nano-particle plays critical
Influence.And the synthetic method report of the FeOOH nano-particles of spheroidal is very few, and its size adjustable is even more and is rarely reported.
The content of the invention
FeOOH nano-particle it is an object of the invention to provide a kind of size adjustable and preparation method thereof, the preparation
Pass through first by iron salt hydrolysis in method, be subsequently added into carboxylate and combined with iron ion with providing band carboxyl；Meanwhile, add basic species
Matter is eventually adding urea so that system is in alkalescence adjusting the pH value of solution, is finally heated, cooled down and purifying obtains hydroxyl
Iron oxide (FeOOH) nano-particle.
To achieve these goals, the invention provides the preparation of the FeOOH nano-particle of kind size adjustable
Method, wherein, the preparation method includes：First by molysite, be dissolved in obtained solution in solvent；Then by carboxylate, alkaline matter
While in adding the solution；Again to addition urea in the solution with prepared mixed liquor；Finally the mixed liquor is added
Heat treatment, natural cooling are that the FeOOH nano-particle is obtained.
Present invention also offers a kind of FeOOH nano-particle of the size adjustable as obtained in above-mentioned preparation method.
By above-mentioned technical proposal, select, first by iron salt hydrolysis, to be subsequently adding carboxylate in the present invention, using carboxylate radical band
Negative electrical charge makes it be combined with iron ion, recycles alkaline matter with the pH of regulation system, then is added in system by urea
Water-filling solution is so that the system of obtaining is in alkalescence；Finally heated, obtained sediment is hydroxyl oxygen after cooling, centrifugal purification
Change Fe nanometer particles.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the characterization result figure for detecting example 2；
Fig. 2 is detected in example 1 to the transmission electron microscope phenogram of A6；
Fig. 3 is detected in example 1 to the high-resolution-ration transmission electric-lens phenogram of A6；
Fig. 4 is detected in example 1 to the transmission electron microscope phenogram of A1-A9；
Fig. 5 is detected in example 1 to the transmission electron microscope phenogram of A10-A18；
Fig. 6 is the energy spectrum diagram of Fe 2p tracks in the characterization result for detect example 3；
Fig. 7 is the energy spectrum diagram of O1s tracks in the characterization result for detect example 3；
Fig. 8 is the characterization result figure for detecting example 4；
Fig. 9 is the characterization result figure for detecting example 5；
Figure 10 is the transmission electron microscope phenogram of B1 obtained in comparative example 1；
Figure 11 is the transmission electron microscope phenogram of B2 obtained in comparative example 2；
Figure 12 is the transmission electron microscope phenogram of B3 obtained in comparative example 3；
Figure 13 is the transmission electron microscope phenogram of B4 obtained in comparative example 4.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, there is provided a kind of preparation method of the FeOOH nano-particle of size adjustable, the preparation method
Including：First by molysite, be dissolved in obtained solution in solvent；Then in carboxylate, alkaline matter being added into the solution simultaneously；Again to
Add urea that mixed liquor is obtained in the solution；Finally the mixed liquor is heated, natural cooling, centrifugal purification
The FeOOH nano-particle is obtained afterwards.
In above-mentioned preparation method, the weight proportion of the molysite, solvent, carboxylate and urea can be in scope wide
Interior selection, but prepare yield in order to further improve FeOOH nano-particle, it is preferable that the molysite, solvent, carboxylic
The weight proportion of hydrochlorate and urea is 1-9：104：10-15：12-48.
In the present invention, molysite used can be selected in scope wide, but in order to further improve FeOOH
Nano-particle prepares yield, it is preferable that the molysite is ferric sesquichloride, ferrous sulfate or frerrous chloride.
In a particular embodiment, solvent species used can be selected in a wide range, but in order to promote
The hydrolysis of molysite is to promote ferric iron to be hydrolyzed into iron hydroxide and hydrogen ion, it is preferable that the solvent is that water, ethylene glycol or two are sweet
One or more of alcohol.
In the present invention, carboxylate be added to provide carboxylic acid ion to system and combined with iron ion, therefore carboxylic
Hydrochlorate can be selected in a wide range, but prepare yield in order to improve FeOOH nano-particle, it is preferable that institute
It is one or more in sodium citrate, sodium acetate or sodium tartrate to state carboxylate.
In a specific embodiment, the pH of system is adjusted using alkaline matter, alkaline matter used can be
Selected in scope wide, but in order to be more beneficial for the regulation of system pH, it is preferable that the alkaline matter is hydroxide
At least one of sodium, sodium carbonate, potassium hydroxide or ammoniacal liquor；
Or, the alkaline matter be sodium hydroxide solution, sodium carbonate liquor, potassium hydroxide solution or ammoniacal liquor at least
One.
In the present invention, the pH value of system can be controlled in a wide range, but in order to further improve hydroxyl oxygen
That changes Fe nanometer particles prepares yield, it is preferable that after the alkaline matter is added, and the pH of system is 4.0-8.0.
In addition, the condition of the heating in the present invention in preparation process can be selected in scope wide, but in order to
That improves FeOOH nano-particle prepares yield and reaction rate, it is preferable that the temperature of the heating is 110-125
DEG C, the time is 6-30h.
A kind of FeOOH nano-particle of the size adjustable as obtained in above-mentioned preparation method is additionally provided in the present invention；
And the FeOOH nano-particle is spheroidal, and the particle diameter of the FeOOH nano-particle is 2-90nm.
Below will the present invention will be described in detail by embodiment.
In following examples, scanning electron microscope (SEM) photograph is obtained by the sem test of Japanese HITACHI companies S-480 models
Arrive；Transmission electron microscope picture is obtained by the transmissioning electric mirror test of Japanese HITACHI companies HT-7700 models；X-ray photoelectron energy
Spectrogram (XPS) is to test to obtain by the x-ray photoelectron spectroscopy of the models of Perkin Elmer companies of U.S. PHI 5600；Fu
In leaf infrared spectrogram (FT-IR) be to be surveyed by the Fourier infrared spectrograph of PerkinElmer companies of U.S. PE-983 models
Examination is obtained；The x-ray powder diffraction instrument that X-ray powder diffraction figure (XRD) passes through the XRD-7000 models that Japanese Shimadzu is produced is surveyed
Examination is obtained.
Raw material ferric sesquichloride is the commercially available product for being purchased from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group；Sodium citrate is Shanghai
The commercially available product of Ling Feng chemical reagent Co., Ltd；Urea is the commercially available product of Sigma-Aldrich reagents Co., Ltd；NaOH
It is the commercially available product of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
First by ferric sesquichloride (ferric chloride hexahydrate), be added to the water obtained solution；Then by sodium citrate, NaOH
While (pH of solution is adjusted to 4.0) in adding the solution；Again to addition urea in the solution with prepared mixed liquor；Most
The mixed liquor is heated into 6h at 120 DEG C afterwards, natural cooling, after, be by volume 1 by gained FeOOH and isopropanol：3
Mixing, is centrifuged under being 10000 turns in rotating speed and is purified for 10 minutes, and gained precipitation is scattered in isometric water, that is, institute is obtained
FeOOH nano-particle is stated, A1 is designated as；
Wherein, the weight proportion of ferric sesquichloride used, water, sodium citrate and urea is 5：104：10：30.
Embodiment 2
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A2；The difference is that being heated at 120 DEG C
10h。
Embodiment 3
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A3；The difference is that being heated at 120 DEG C
14h。
Embodiment 4
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A4；The difference is that being heated at 120 DEG C
18h。
Embodiment 5
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A5；The difference is that being heated at 120 DEG C
20h。
Embodiment 6
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A6；The difference is that being heated at 120 DEG C
24h。
Embodiment 7
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A7；The difference is that being heated at 120 DEG C
26h。
Embodiment 8
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A8；The difference is that being heated at 120 DEG C
28h。
Embodiment 9
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as A9；The difference is that being heated at 120 DEG C
30h。
Embodiment 10
First by ferric sesquichloride, be added to the water obtained solution；Then sodium citrate, NaOH are added simultaneously described molten
In liquid, the pH of system is adjusted to 4.0, then to addition urea in the solution with prepared mixed liquor；Finally by the mixed liquor
120 DEG C heat 24h, natural cooling, then by obtained FeOOH nano-particle and isopropanol by volume be 1：3 mix
Close, carry out centrifugation under being 10000 turns in rotating speed is purified for 10 minutes, and gained precipitation is scattered in isometric water, that is, be obtained
The FeOOH nano-particle, is designated as A10；
Wherein, the weight proportion of ferric sesquichloride used, water, sodium citrate and urea is 9：104：15：48.
Embodiment 11
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as A11, unlike, the pH of system is adjusted
Save to 4.5.
Embodiment 12
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as A12, unlike, the pH of system is adjusted
Save to 5.0.
Embodiment 13
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as unlike A13, the pH of system being adjusted
Save to 5.3.
Embodiment 14
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as unlike A14, the pH of system being adjusted
Save to 5.5.
Embodiment 15
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as unlike A15, the pH of system being adjusted
Save to 5.7.
Embodiment 16
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as unlike A16, the pH of system being adjusted
Save to 6.0.
Embodiment 17
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as unlike A17, the pH of system being adjusted
Save to 7.0.
Embodiment 18
The method of case embodiment 9 is obtained FeOOH nano-particle, is denoted as unlike A18, the pH of system being adjusted
Save to 8.0.
Comparative example 1
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as B1, unlike, the temperature of heating is 100
DEG C, the heat time is 24h.
Comparative example 2
Method according to embodiment 1 is obtained FeOOH nano-particle, is designated as B2, unlike, the temperature of heating is
140 DEG C, the time of heating is 24h.
Comparative example 3
Method according to embodiment 10 is obtained FeOOH nano-particle, is designated as B3, unlike, the pH of system is adjusted
Save to 3.5.
Comparative example 4
Method according to embodiment 10 is obtained FeOOH nano-particle, is designated as B3, unlike, the pH of system is adjusted
Save to 8.5.
Detection example 1
By the transmission electron microscope of HT-7700 models to obtained FeOOH nano-particle A1-A18 in embodiment 1-18
Morphology characterization is carried out, and high-resolution-ration transmission electric-lens sign is carried out to A6；
Wherein, Fig. 2 is shown in the projection characterization result for implementing FeOOH nano-particle A6 obtained in 6；To the high score of A6
Distinguish that transmission electron microscope characterization result is shown in Fig. 3；Projection phenogram to A1-A9 is shown in Fig. 4；The characterization result of A10-A18 is shown in Fig. 5.
Morphology characterization equally is carried out to FeOOH nano-particle B1-B4 obtained in comparative example 1-4, be specifically shown in Figure 10-
13。
Detection example 2
FeOOH nano-particle A6 obtained in embodiment 6 is carried out by pattern table by the ESEM of S-4800 models
Levy, be specifically shown in Fig. 1.
Detection example 3
By the x-ray photoelectron spectroscopy of the models of Perkin Elmer companies of U.S. PHI 5600 to being made in embodiment 6
The elemental distribution of the FeOOH A6 for obtaining is characterized, and is specifically shown in Fig. 6 and Fig. 7.
Detection example 4
By the x-ray powder diffraction instrument of Japanese Shimadzu Corporation XRD-7000 models to obtained hydroxyl oxygen in embodiment 6
Changing iron A6 carries out the sign of crystal formation, is specifically shown in Fig. 8.
Detection example 5
Select with pure KBr as blank, by the Fourier of PerkinElmer companies of U.S. PE-983 models
Infrared spectrometer (FT-IR) carries out the sign of functional group's species to obtained FeOOH A6 in embodiment 6, is specifically shown in Fig. 9.
Above by the detection for obtained FeOOH nano-particle A6 in embodiment 6 detect example 1-5, and
Every testing result shows：
According to Fig. 1,2, it can be seen that embodiment 6 do obtained FeOOH nano-particle from pattern from, be obtained
Nanoparticle Size it is homogeneous, be evenly distributed, regular shape, and in approximate sphericity, the smooth of the edge, with good dispersiveness.
The cluster being made up of multiple nano particles the clearly visible prepared FeOOH nano-particles of Fig. 1, average-size is about
30nm。
In addition, the structure in order to clearly illustrate nano particle, enters under the high magnification of transmission scanning electron microscope to sample A6
Row Electronic Speculum is imaged, as a result as shown in Figure 3；While the crystal structure in order to study prepared FeOOH nano-particle, I
High resolution analysis is carried out to sample.Interplanar distance about 0.254nm is obtained according to Fig. 3 is measurable, this result has corresponded to hydroxyl
(211) crystal face of base ferric oxide nano particles (FeOOH).
Morphology characterization according to Fig. 1-3 is as a result, it is possible to the nano-particle A6 synthesized in preliminary proof embodiment 6 is hydroxyl oxygen
Change Fe nanometer particles.
It is FeOOH nano-particle to further prove synthesized nano-particle A6, detection example has been carried out to A6
The detection of 3-5, testing result is as Figure 6-9；According to Fig. 6 can, it is evident that in obtained nano-particle A6,
There is spectral peak at 711.1 and 725.4eV, the two peaks match with the peak of the oxidation state of the Fe2p of FeOOH nano-particles.Separately
Outward, two spectral peaks from Fig. 7 at 531.1 and 530.0eV, also demonstrate that the presence of-OH and-O-.Therefore, example 3 pairs is detected
The x-ray photoelectron power spectrum test result of A6 nano-particles also demonstrates obtained A6 as FeOOH nano-particles.
Additionally, Fig. 8 is the X-ray powder diffraction figure of A6,16.90 ° in Fig. 8,26.87 °, 35.05 °, 40.00 °,
The peak existed at 44.00 °, 52.33 °, 55.40 °, 61.94 ° and 74.66 ° and (200) face, (130) of FeOOH nano-particles
Face, (211) face, (301) face, (150) face, (600) face, (620) face, (611) face and (242) face match, referring to (JCPDS
no.75-1594).Lattice, crystal face in the characterization result of Fig. 8 and Fig. 3 are also consistent.
Fig. 9 is the FTIR spectrum figure of A6, in 3420cm in Fig. 9-1At position, it is shown that obvious O-H's is flexible
Vibration peak.In 1610cm-1At position, it is shown that the flexural vibrations peak of H-O-H, and in 1060cm-1At position, it is shown that
The flexural vibrations peak of the O-H of FeOOH nanoparticle surfaces.These all demonstrate the presence of A6 nanoparticle surface hydroxyls.Meanwhile,
In 852cm-1Peak at position, and the flexural vibrations peak of Fe-O-H matches.And in 665cm-1Peak at position, with Fe-O
Fe-OH symmetrical stretching vibrations or lattice vibration it is consistent.
Above in the testing result in detection example 1-5, the FeOOH nano-particle A6 according to obtained by Fig. 1-3 couples enters
The result of row morphology characterization, and the further characterization result of Fig. 6-9 demonstrates FeOOH nano-particle in embodiment 6
A6's is successfully prepared.
Equally, obtained FeOOH nano-particle A1-5 and A10-A18 in embodiment 1-5 and 10-18 are entered
The detection of row detection example 1-5, testing result is basically identical with the testing result of A6.
Additionally, being also carried out detecting the detection of example 2 to the nano-particle B1-B4 obtained by comparative example 1-4, testing result is such as
Shown in Figure 10-13；Be will be obvious that according to Figure 10-13, when synthesis temperature is less than 110 DEG C or higher than 125 DEG C, obtained receives
Rice corpuscles particle diameter heterogeneity, and it is uneven to dissipate property.In addition, when the pH of system is less than 4.0 or more than 8.0, obtained nanometer
Particle blur margin is clear, and particle size differs, and pH is small be more than 8.0 when in addition spherical nano-particle can not be formed.Cause
This, prepares in the building-up process of spherical FeOOH nano-particle, and the temperature of heating is 110-125 DEG C, and the time is 6-
30h, and the pH of system is 4.0-8.0, the particle diameter of obtained FeOOH nano-particle is 2-90nm.
In addition, in the present invention, having probed into hydroxyl oxidations of the pH of the time and system heated in building-up process to synthesizing
The influence of the particle diameter of Fe nanometer particles：
In embodiment 1-9, the pH of solution is controlled to adjust to 4.0, the temperature of heating is that 120 DEG C and chlorination used are high
The weight proportion of iron, water, sodium citrate and urea is 5：104：10：30；Only change heating time from 6h, 10h, 14h, 18h,
20h, 24h, 26h, 28h to 30h, and changed by the pattern that radio mirror characterizes obtained nano-particle A1-A9, such as Fig. 4 institutes
Show.From fig. 4, it can be seen that be consistent in its dependent variable, in the case of only changing the temperature of heating, with the increase of heat time,
Its size increases therewith, and finally, about when the time of heating being 24h, the crystal growth of nano-particle reaches balance, and size is not
Change again.Because being made up of two processes of forming core and growth in crystallization process, in crystallization, first have in mother
The nucleus with certain size (critical dimension) is formed in body fluid, then the atom on these nucleus constantly in cohesion mother liquor and
Growth, so as to constantly carrying out with synthetic reaction so that nano material constantly grows.
In embodiment 10-18, the temperature for controlling the heating of solution is 120 DEG C and ferric sesquichloride used, water, lemon
The weight proportion of sour sodium and urea is 9：104：15：48, only change the pH of system from 4.0,4.5,5.0,5.3,5.5,5.7,
6.0th, 7.0 to 8.0, and changed by the pattern that radio mirror characterizes obtained nano-particle A10-A18, as shown in Figure 5.
According to Fig. 5：It can be seen from classical crystal growth condition, crystallization process is by two process institute groups of forming core and growth
Into.It is the quantity and nucleation speed that nucleus is controlled by controlling to adjust the pH value of system in the present invention.Because hydroxyl oxygen
The vital factor for changing the formation of Fe nanometer particles is exactly FeCl3Hydrolysis, and the pH value of system is to FeCl3It is hydrolyzed
Journey has a great impact.Fig. 5 has intuitively reflected influence of the pH value to the size of FeOOH nano-particle：With pH value
Increase, particle size reduces therewith.Main cause has at following 2 points：1).FeCl3Hydrolysis, make solution in acidity, acidity increase
It is strong then be unfavorable for FeCl3Hydrolysis so that particle nucleation is slower, less, easily form larger particle.Conversely, alkalescence enhancing, profit
In FeCl3Hydrolysis so that particle nucleation is very fast, more, easily form less particle.2) raw materials have citrate, synthesis
Particle is negatively charged.As the increase of system pH, hydroxyl increase, anions gradually increase, and negative electrical charge increases, its
The value of potential gradually increases, and electrostatic repulsion forces increase therewith, and particle is difficult accumulation and grows up, and causes particle gradually less to being formed
Particle direction is developed.
Therefore, under conditions of pH value is regulated and controled, with the gradually increase of pH value, particle size is gradually reduced.
In sum, heating such as can gradually be increased by adjusting the time heated in building-up process in the present invention
Time can cause the FeOOH nano-particle ground particle diameter of synthesis increasing, but after the heat time is more than 24h, particle diameter is several
Maintain stabilization and do not continue to increase；And during the pH value of regulation system, with the rising of pH value, obtained FeOOH
Nano-particle ground particle diameter is less and less, and this is that anions are gradually because with the increase of system pH, hydroxyl increases
Increase, negative electrical charge increases, the value of its potential gradually increases, and electrostatic repulsion forces increase therewith, particle is difficult accumulation and grows up, and causes grain
Son gradually develops to the less particle direction of formation.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. the preparation method of the FeOOH nano-particle of a kind of size adjustable, it is characterised in that the preparation method includes：
First by molysite, be dissolved in obtained solution in solvent；Then in carboxylate, alkaline matter being added into the solution simultaneously；Again to described
Add urea that mixed liquor is obtained in solution；Finally the mixed liquor is heated, after natural cooling, centrifugal purification i.e.
The FeOOH nano-particle is obtained.
2. the preparation method according to claim 1, wherein, the weight ratio of the molysite, solvent, carboxylate and urea is
1-9：104：10-15：12-48.
3. preparation method according to claim 2, wherein, the molysite is ferric sesquichloride, ferrous sulfate or frerrous chloride.
4. preparation method according to claim 3, wherein, the solvent be one kind in water, ethylene glycol or diethylene glycol (DEG) or
It is various.
5. preparation method according to claim 3, wherein, the carboxylate is sodium citrate, sodium acetate or sodium tartrate
In one or more.
6. the preparation method according to any one in claim 1-5, wherein, the alkaline matter is NaOH, carbon
At least one of sour sodium, potassium hydroxide or ammoniacal liquor；
Or, the alkaline matter is at least in sodium hydroxide solution, sodium carbonate liquor, potassium hydroxide solution or ammoniacal liquor
Person.
7. preparation method according to claim 6, wherein, after the alkaline matter is added, the pH of system is 4.0-
8.0。
8. preparation method according to claim 7, wherein, the temperature of the heating is 110-125 DEG C, and the time is 6-
30h。
9. the FeOOH nano-particle of a kind of size adjustable, it is characterised in that the FeOOH nano-particle is by weighing
Profit requires that the preparation method in 1-8 described in any one is obtained.
10. FeOOH nano-particle according to claim 9, wherein, the FeOOH nano-particle is circle
It is spherical, and the particle diameter of the FeOOH nano-particle is 2-90nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710169820.7A CN106904657B (en) | 2017-03-21 | 2017-03-21 | FeOOH nano-particle of size adjustable and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710169820.7A CN106904657B (en) | 2017-03-21 | 2017-03-21 | FeOOH nano-particle of size adjustable and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106904657A true CN106904657A (en) | 2017-06-30 |
| CN106904657B CN106904657B (en) | 2018-08-17 |
Family
ID=59195099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710169820.7A Active CN106904657B (en) | 2017-03-21 | 2017-03-21 | FeOOH nano-particle of size adjustable and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106904657B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314087A (en) * | 2018-03-12 | 2018-07-24 | 清华大学 | A kind of preparation method and applications of the super particle of unformed FeOOH |
| CN109967090A (en) * | 2019-04-29 | 2019-07-05 | 安徽师范大学 | The nanocomposite and its preparation method and application of Au@FeOOH SPs heterojunction structure |
| CN110026195A (en) * | 2019-05-05 | 2019-07-19 | 河北师范大学 | A kind of high activity α-Fe2O3Nanometer sheet and its preparation method and application |
| CN110064371A (en) * | 2019-04-18 | 2019-07-30 | 华东师范大学 | A kind of adsorbent and preparation method and application removing water body inorganic arsenic |
| CN110787307A (en) * | 2019-12-16 | 2020-02-14 | 安徽师范大学 | Magnetic resonance imaging nano contrast agent and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4822915B1 (en) * | 1967-02-08 | 1973-07-10 | ||
| JPS5951495B2 (en) * | 1976-03-10 | 1984-12-14 | 日立マクセル株式会社 | Production method of β-iron oxyhydroxide |
| CN101428863A (en) * | 2008-11-27 | 2009-05-13 | 天津大学 | Process for producing spherical FeOOH nano-powder |
| CN101475222A (en) * | 2009-01-22 | 2009-07-08 | 中国科学院上海硅酸盐研究所 | Iron oxide hollow microsphere and preparation thereof |
| CN103204548A (en) * | 2013-04-12 | 2013-07-17 | 陕西科技大学 | Method of controllably preparing narrow particle size distribution submicron order alpha-FeOOH |
| CN106430324A (en) * | 2016-09-08 | 2017-02-22 | 合肥学院 | Flowerlike alpha-FeOOH porous micro-nanospheres and preparation method thereof |
-
2017
- 2017-03-21 CN CN201710169820.7A patent/CN106904657B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4822915B1 (en) * | 1967-02-08 | 1973-07-10 | ||
| JPS5951495B2 (en) * | 1976-03-10 | 1984-12-14 | 日立マクセル株式会社 | Production method of β-iron oxyhydroxide |
| CN101428863A (en) * | 2008-11-27 | 2009-05-13 | 天津大学 | Process for producing spherical FeOOH nano-powder |
| CN101475222A (en) * | 2009-01-22 | 2009-07-08 | 中国科学院上海硅酸盐研究所 | Iron oxide hollow microsphere and preparation thereof |
| CN103204548A (en) * | 2013-04-12 | 2013-07-17 | 陕西科技大学 | Method of controllably preparing narrow particle size distribution submicron order alpha-FeOOH |
| CN106430324A (en) * | 2016-09-08 | 2017-02-22 | 合肥学院 | Flowerlike alpha-FeOOH porous micro-nanospheres and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314087A (en) * | 2018-03-12 | 2018-07-24 | 清华大学 | A kind of preparation method and applications of the super particle of unformed FeOOH |
| CN108314087B (en) * | 2018-03-12 | 2019-11-08 | 清华大学 | A kind of preparation method and applications of the super particle of unformed FeOOH |
| CN110064371A (en) * | 2019-04-18 | 2019-07-30 | 华东师范大学 | A kind of adsorbent and preparation method and application removing water body inorganic arsenic |
| CN110064371B (en) * | 2019-04-18 | 2021-10-15 | 华东师范大学 | Adsorbent for removing inorganic arsenic in water body and preparation method and application thereof |
| CN109967090A (en) * | 2019-04-29 | 2019-07-05 | 安徽师范大学 | The nanocomposite and its preparation method and application of Au@FeOOH SPs heterojunction structure |
| CN109967090B (en) * | 2019-04-29 | 2021-09-28 | 安徽师范大学 | Nano composite material with Au @ FeOOH SPs heterostructure as well as preparation method and application of nano composite material |
| CN110026195A (en) * | 2019-05-05 | 2019-07-19 | 河北师范大学 | A kind of high activity α-Fe2O3Nanometer sheet and its preparation method and application |
| CN110026195B (en) * | 2019-05-05 | 2021-09-03 | 河北师范大学 | High-activity alpha-Fe2O3Nanosheet and preparation method and application thereof |
| CN110787307A (en) * | 2019-12-16 | 2020-02-14 | 安徽师范大学 | Magnetic resonance imaging nano contrast agent and preparation method and application thereof |
| CN110787307B (en) * | 2019-12-16 | 2022-04-12 | 安徽师范大学 | Magnetic resonance imaging nano contrast agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106904657B (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106904657B (en) | FeOOH nano-particle of size adjustable and preparation method thereof | |
| Yusoff et al. | Synthesis and characterization of biocompatible Fe3O4 nanoparticles at different pH | |
| Yew et al. | An eco-friendly means of biosynthesis of superparamagnetic magnetite nanoparticles via marine polymer | |
| Bagherzadeh et al. | Morphology Modification of the Iron Fumarate MIL‐88A Metal–Organic Framework Using Formic Acid and Acetic Acid as Modulators | |
| Xu et al. | Seedless synthesis of high aspect ratio gold nanorods with high yield | |
| Zhang et al. | Solvothermal synthesis of magnetic Fe3O4 microparticles via self-assembly of Fe3O4 nanoparticles | |
| Azcona et al. | Simple and novel strategies to achieve shape and size control of magnetite nanoparticles intended for biomedical applications | |
| CN103347543B (en) | It is coated with the preparation method of the ferric oxide nanometer particle of water wetted material and uses its magnetic resonance imaging contrast | |
| Huang et al. | Physicochemical and structural characteristics of nano eggshell calcium prepared by wet ball milling | |
| Haldorai et al. | Supercritical fluid mediated synthesis of poly (2-hydroxyethyl methacrylate)/Fe3O4 hybrid nanocomposite | |
| CN111834074B (en) | For Fe taking oleic acid as ligand3O4Method for purifying nano particles and synthesizing magnetic nano stirrer and application | |
| Xu et al. | The synthesis of size-adjustable superparamagnetism Fe 3 O 4 hollow microspheres | |
| Chen et al. | Controlled synthesis of Fe3O4 nanosheets via one-step pyrolysis of EDTA ferric sodium salt | |
| Srinivasan et al. | Functionalization of magnetic nanoparticles with organic molecules: Loading level determination and evaluation of linker length effect on immobilization | |
| Low et al. | A facile and rapid sonochemical synthesis of monodispersed Fe3O4@ cellulose nanocrystal nanocomposites without inert gas protection | |
| Altiner et al. | Ultrasonic-assisted production of precipitated calcium carbonate particles from desulfurization gypsum | |
| CN105289456B (en) | A kind of superparamagnetic Fe3O4The preparation method and application of nano material | |
| Sohrabijam et al. | Prepartion and characterization of superparamagnetic chitosan coated maghemite (γ-Fe2O3) for gene delivery | |
| Palanikumar et al. | Effect of folic acid decorated magnetic fluorescent nanoparticles on the sedimentation of starch molecules | |
| CN113680314A (en) | Fly ash loaded nano spherical magnesium hydroxide composite material and preparation method and application thereof | |
| JP2011236089A (en) | Surface-modified spherical silica powder and method for producing the same | |
| Yelenich et al. | Synthesis and properties of AFe 2 O 4 (A= Mn, Fe, Co, Ni, Zn) nanoparticles produced by deposition from diethylene glycol solution | |
| CN111620381A (en) | beta-FeOOH nano rod and preparation method thereof | |
| CN110550666A (en) | Monodisperse and superparamagnetic ferroferric oxide nanoflower and preparation method thereof | |
| Wang et al. | A room temperature solution-phase process to synthesize pure phase single-crystalline hexagonal cobalt hydroxide nanoplates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |