CN105032342B - A kind of effective layered bi-metal oxide adsorbent preparation method for removing low phosphorus acid group - Google Patents
A kind of effective layered bi-metal oxide adsorbent preparation method for removing low phosphorus acid group Download PDFInfo
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Abstract
The invention discloses a kind of effective layered bi-metal oxide adsorbent preparation method and applications for removing low phosphorus acid group.The present invention is first with hydrophobic ionic liquid BmimPF6For oil phase, with N, N dimethylformamides (DMF) are the BmimPF of cosolvent6/DMF/H2In the anti-phase surfactant-free microemulsion system of O ionic liquid bag water, the ultra-thin stratiform duplex metal hydroxide nanometer piece presoma of small particle is prepared using double microemulsion coprecipitation methods, then 500 DEG C of high temperature are calcined in air atmosphere, prepare layered bi-metal oxide adsorbent.The specific surface area of gained layered bi-metal oxide is 107.36~158.46m2/ g, aperture is 8.56~11.17nm, and pore volume is 0.358~0.468cm3/g；It is about the homogeneous layered duplex metal hydroxide nanometer piece of 5nm, particle diameter distribution that particle diameter can be recovered to be formed in aqueous medium for 150~200nm, thickness；Its adsorption rate to low phosphorus acid group is far above bulky grain houghite prepared by its presoma layered double hydroxide and traditional co-precipitation method.
Description
Technical field：
The present invention relates to it is a kind of it is effective remove low phosphorus acid group layered bi-metal oxide adsorbent preparation method, with
And the present invention relates to adsorption applications of the layered bi-metal oxide adsorbent obtained by preparation method to low phosphorus acid group in water body,
Belong to field of nanometer material technology.
Background technology：
The development modernized with industrial or agricultural, the nutriment such as a large amount of nitrogen, phosphorus enters water body with sewage so that coastal waters and lake
There is eutrophication in pool water body, causes algae and other planktonic organisms to breed rapidly, causes water quality deterioration, aquatile big
The consequences such as death are measured, the ecosystem is not only destroyed, and the toxin produced can threaten human health by food chain.Research shows
Phosphorus is the crucial governing factor of body eutrophication, and when its concentration is higher than 0.03mg/L, the eutrophication of water body may result in
Red tide or wawter bloom occur.Therefore, the content of phosphorus in waste discharge is effectively reduced to suppressing body eutrophication, prevention red tide or water
Grey hair life is significant.The method of domestic and international waste water dephosphorization mainly has bioanalysis, absorption method, chemical precipitation method, crystallisation
With ion-exchange and ecological method etc., wherein equipment is simple, easy to operate, do not produce secondary pollution because it has for absorption method
The advantages of, gain great popularity, and clay mineral because its have unique layer structure, big specific surface area, good absorption and from
Sub- switching performance, and rich reserves, cheap, nontoxic to environment, regenerating easily, as new and effective adsorption material
Material is widely applied [Zhou J, Yang S, Yu J, Shu Z.Novel hollow in waste water dephosphorization field
microspheres of hierarchical zinc–aluminum layered double hydroxides and
their enhanced adsorption capacity for phosphate in
water.J.Hazard.Mater.2011,192,1114–1121.]。
Layered double hydroxide (Layered Double Hydroxides, LDH) is an anionoid clay, its
Formula is [M1-x 2+Mx 3+(OH)2]x+(An-)x/n·mH2O, wherein M (OH)6Octahedron shares rib and open lamella accumulation is presented
Structure, each octahedral unit is formed by the central metallic ions M of hexa-coordinate and the OH- positioned at summit.Due to part M2+By M3+
Substitution can make lamella band structure positive charge, and interlayer, which has tradable anion, makes electric charge reach balance.The engaging force of LDH interlayers
It is weaker, mezzanine space high resilience, with spies such as larger surface area, higher ion exchange capacity and excellent heat endurances
Point, very strong capture ability is shown to organic and inorganic anion.But LDH can produce non-ization after being calcined at 400~800 DEG C
The layered bi-metal oxide (LDO) of metering is learned, due to LDH " memory effect ", calcined product LDO is in the water containing pollutant
It is hydrated in solution, recovers that anionic pollutant is inserted into interlayer during LDH again, thus is held with higher absorption
Measure [Cai P, Zheng H, Wang C, Ma H, Hu J, Pu Y, Liang P.Competitive adsorption
characteristics of fluoride and phosphate on calcined Mg-Al-CO3layered double
hydroxides.J.Hazard.Mater.2012,213-214,100-108.].It is useless that current LDH and LDO is successfully used for discharge
The removal of silver orthophosphate in water, seawater.But conventional method prepare obtained by LDH particle diameters it is larger and pattern is uncontrollable, and when using
Easily assemble, obtained calcined product LDO is not fully exerted to the absorption property of pollutant, therefore, improve
Presoma LDH surface area, increase adsorption site and adsorption capacity, has great significance to developing efficient LDO adsorbents.
Reverse micro emulsion is typically that countless " small water droplet " is dispersed in oil-continuous phase, the isotropism of formation, transparent
With thermodynamically stable dispersion, it is made up of in appropriate proportions components such as water, oil, surfactant and cosurfactants.
These stable each " small water droplets " for separating each other are a microreactors, possess very big interface, its is adjustable
Size can not only control nucleation and the growth of nano-particle, and can also control the size of particle, it is considered to be controllable preparation
The excellent medium of inorganic nano-particle.All contain surfactant in conventional inverter microemulsion, received using their the inorganic of preparation
Rice corpuscles is all mixed with surfactant bar none, and when preparing LDH especially with reverse micro emulsion, surfactant can be with
Anionic form is intercalation into its interlayer, or absorption in surface [Hu G, O ' the Hare D.Unique layered of stratified material
double hydroxide morphologies using reverse microemulsion synthesis,
J.Am.Chem.Soc.2005,127,17808-17813.], secondary pollution can be caused when using gained sorbing material, and
Also make that the regenerative process of sorbing material is extremely cumbersome, cost is higher.
Research shows, in the presence of no surfactant, and some three component systems can also form microemulsion, this kind of micro emulsion
Liquid is referred to as surfactant-free microemulsion (Surfactant-free Microemulsion, SFME).Using SFME system systems
Standby LDH, can not only control the LDH particles that Nanoparticle Size, particle size distribution range are narrow, raising is dispersed, obtain to be not present
Impurity pollutes, and component is simple, easy to operate, the problem of fundamentally solving to exist when classical microemulsion prepares LDH, simultaneously
Also new thinking is provided to prepare efficient LDO adsorbents.But, with hydrophobic ionic liquid BmimPF6For oil phase, with N,
Dinethylformamide (DMF) is the BmimPF of cosolvent6/DMF/H2First prepared in the anti-phase SFME systems of O ionic liquid bag water small
The ultra-thin LDH nanometer sheets of particle diameter, then high-temperature calcination prepares LDO again, and uses it for low concentration Phosphateadsorption in water body
Correlative study has not been reported.
The content of the invention：
In view of the shortcomings of the prior art and this area research and application demand, have it is an object of the invention to provide one kind
Effect removes the layered bi-metal oxide adsorbent preparation method of low phosphorus acid group.First with hydrophobic ionic liquid
BmimPF6For oil phase, with the BmimPF that DMF (DMF) is cosolvent6/DMF/H2O ionic liquid bag water is anti-phase
In SFME systems, the ultra-thin LDH nanometer sheets of small particle, then 500 DEG C of high-temperature calcinations again are prepared in double microemulsion coprecipitation methods
Prepare the layered bi-metal oxide adsorbent that specific surface area is big, absorption property is high.
A kind of preparation method for layered bi-metal oxide adsorbent that the present invention is provided, is first coprecipitated using double microemulsions
Shallow lake method prepares its presoma layered double hydroxide, then carries out high-temperature calcination to it again and prepares layered bi-metal oxidation
Thing, specifically includes following steps：
1) MgCl is weighed respectively2·6H2O and AlCl3·9H2O, adds deionized water, prepares total concentration of metal ions and is
0.05~3.0mol/L MgCl2And AlCl3Mixed-salt aqueous solution；N, N- dimethyl formyls are added into the mixing salt solution
Amine DMF and hydrophobic ionic liquid BmimPF6, wherein mixed-salt aqueous solution, DMF and BmimPF6Volume ratio be 2~15：30~
50：40~70,30~60min of magnetic agitation, treats that solution is changed into transparent from muddiness, has prepared reverse micro emulsion A at room temperature；
2) ammoniacal liquor that certain volume concentration is 25% is taken, DMF and BmimPF is added thereto6, wherein 25% ammoniacal liquor,
DMF and BmimPF6Volume ratio be 2~15：30~50：40~70,30~60min of magnetic agitation, treats solution by mixing at room temperature
It is turbid to be changed into transparent, prepare reverse micro emulsion B；
3) under the conditions of magnetic agitation, reverse micro emulsion A and reverse micro emulsion B is titrated simultaneously, control pH 9.0~
Between 10.0, reaction 12h is stirred at room temperature, afterwards 10~24h of aging under the conditions of 25~75 DEG C, gained slurries turn in 10000rpm
The lower centrifugation 10min of speed, is washed 2 times, dries 12 hours, obtain under 60 DEG C of vacuum respectively with DMF, absolute ethyl alcohol and deionized water successively
The ultra-thin stratiform bimetallic oxide nanometer sheet of presoma small particle；
4) by step 3) obtained by the ultra-thin stratiform duplex metal hydroxide nanometer piece dry powder of presoma small particle be put into Muffle
In stove, calcined 3~8 hours under the conditions of 500 DEG C in air atmosphere, obtain layered bi-metal oxide adsorbent.
Step 1) in MgCl2And AlCl3The total concentration of metal ion is 0.45mol/L, MgCl in mixing salt solution2With
AlCl3Mol ratio be 2：1；The aqueous phase is that the reverse micro emulsion A and aqueous phase of mixed-salt aqueous solution are the anti-phase of ammonia spirit
The aqueous solution, DMF and BmimPF in microemulsion B6Volume ratio it is essentially equal；Step 3) obtained by the ultra-thin stratiform of presoma small particle
The lateral dimension of duplex metal hydroxide nanometer piece is 10~35nm, and average thickness is 0.71nm, by individual layer layered bi-metal hydrogen
Oxide sheets are constituted.
The layered bi-metal oxide specific surface area prepared by above-mentioned preparation method is 107.36~158.46m2/ g, hole
Footpath is 8.56~11.17nm, and pore volume is 0.358~0.468cm3/g。
As the layered bi-metal oxide adsorbent obtained by prepared by above-mentioned preparation method, it can recover to form grain in aqueous medium
Footpath is that 150~200nm, thickness are about the homogeneous layered duplex metal hydroxide nanometer piece of 5nm, particle diameter distribution.
As the layered bi-metal oxide adsorbent obtained by prepared by above-mentioned preparation method, it is suitable for low concentration phosphoric acid in water body
The adsorption applications of root, described application is that layered bi-metal oxide adsorbent is added into the water that phosphate concentration is 2mg/L
In solution, shaken at room temperature reacts 5 hours.
Compared with prior art, main beneficial effect and advantage is the present invention：
1) effective layered bi-metal oxide adsorbent preparation method for removing low phosphorus acid group of the present invention, solution
Traditional co-precipitation method of having determined prepares the aggregation existed during presoma LDH, particle diameter is big, particle size distribution range is wide, specific surface area is small etc.
Defect, presents the features such as particle diameter is small, particle size distribution range is narrow, specific surface area is big, lamella is thin, pore volume is small, correspondingly, high temperature
Calcined product layered bi-metal oxide has the advantages that specific surface area is big, absorption property is high.
2) preparation method of the present invention, the three component Reverse Microemulsion System groups used when preparing presoma LDH
Divide simple, without surfactant, in the absence of the complicated processes for removing surfactant during product purification；Presoma LDH high temperature
Layered bi-metal oxide adsorbent is can be prepared by after calcining, therefore it is simpler to prepare efficient layered bi-metal oxide adsorbent
It is monocyclic to protect.
3) Reverse Microemulsion System of the present invention is ionic liquid bag water reverse micro emulsion, compared to existing micro emulsion
Liquid system, more conforms to the requirement of Green Chemistry.
4) as the layered bi-metal oxide adsorbent obtained by preparation method of the present invention, to low concentration phosphoric acid in water body
The absorption property of root is significantly better than LDH, and preparation method is simple to operate, mild condition, cost are low.
Brief description of the drawings：
Fig. 1 is embodiment 2, the XRD diffraction patterns of the gained sample of comparative example 1~3.
Fig. 2 is embodiment 2, the N of the gained sample of comparative example 1~22Adsorption/desorption isotherms and graph of pore diameter distribution.
Fig. 3 is embodiment 2, the stereoscan photograph of the gained sample of comparative example 1~3.
Fig. 4 is edge in the atomic force microscopy (a) and a figures of the gained layered bi-metal oxide adsorbent of embodiment 2
The crossed section analysis (b) of red straight line.
Embodiment：
To further understand the present invention, the invention will be further described with reference to the accompanying drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1：
1) MgCl is weighed respectively2·6H2O and AlCl3·9H2O, adds deionized water, prepares total concentration of metal ions and is
0.45mol/L, MgCl2And AlCl3Molar concentration rate be 2：1；N,N-dimethylformamide is added into the mixing salt solution
And hydrophobic ionic liquid BmimPF (DMF)6, wherein mixing salt solution, DMF and BmimPF6Volume ratio be 4：48：48, room temperature
Lower magnetic agitation 40min, treats that solution is changed into transparent from muddiness, has prepared reverse micro emulsion A；
2) ammoniacal liquor that certain volume concentration is 25% is taken, DMF and BmimPF is added thereto6, make 25% ammoniacal liquor, DMF
And BmimPF6Volume ratio be 4：48：48, magnetic agitation 40min, treats that solution is changed into transparent from muddiness, prepares at room temperature
Reverse micro emulsion B；
3) under the conditions of magnetic agitation, reverse micro emulsion A and reverse micro emulsion B is titrated simultaneously, control pH 9.0~
Between 10.0, reaction 12h is stirred at room temperature, afterwards the aging 24h under the conditions of 75 DEG C, gained slurries are centrifuged under 10000rpm rotating speeds
10min, is washed 2 times respectively with DMF, absolute ethyl alcohol and deionized water successively, is dried 12 hours under 60 DEG C of vacuum, is obtained presoma small
The ultra-thin stratiform bimetallic oxide nanometer sheet of particle diameter.
4) by step 3) obtained by the ultra-thin stratiform duplex metal hydroxide nanometer piece dry powder of presoma small particle be put into Muffle
In stove, calcined 5 hours under the conditions of 500 DEG C in air atmosphere, obtain layered bi-metal oxide adsorbent, be designated as LDOa。
Embodiment 2：
1) with reference to embodiment 1 step 1) in method and preparation condition, only change mixing salt solution, DMF and BmimPF6's
Volume ratio is 7：46.5：46.5, prepare reverse micro emulsion A；
2) with reference to embodiment 1 step 2) in method and preparation condition, only change mixing salt solution, DMF and BmimPF6's
Volume ratio is 7：46.5：46.5, prepare reverse micro emulsion B；
3) using embodiment 1 step 3) in method and preparation condition, obtain the ultra-thin houghite of presoma small particle and receive
Rice piece；
4) using embodiment 1 step 4) in method and preparation condition, walk obtained presoma small particle in calcining ultra-thin
Acrylic/hydrotalcite-like nano piece, obtains layered bi-metal oxide adsorbent, is designated as LDOb。
Embodiment 3：
1) with reference to embodiment 1 step 1) in method and preparation condition, only change mixing salt solution, DMF and BmimPF6's
Volume ratio is 7：31：62, prepare reverse micro emulsion A；
2) with reference to embodiment 1 step 2) in method and preparation condition, only change mixing salt solution, DMF and BmimPF6's
Volume ratio is 7：31：62, prepare reverse micro emulsion B；
3) using embodiment 1 step 3) in method and preparation condition, obtain the ultra-thin houghite of presoma small particle and receive
Rice piece；
4) using embodiment 1 step 4) in method and preparation condition, walk obtained presoma small particle in calcining ultra-thin
Acrylic/hydrotalcite-like nano piece, obtains layered bi-metal oxide adsorbent, is designated as LDOc。
Embodiment 4：
1) using embodiment 2 step 1) in method and preparation condition, prepared reverse micro emulsion A；
2) using embodiment 2 step 2) in method and preparation condition, prepared reverse micro emulsion B；
3) using embodiment 1 step 3) in method and preparation condition, ageing time is simply reduced to 12h, before obtaining
Drive the ultra-thin acrylic/hydrotalcite-like nano piece of body small particle；
4) using embodiment 1 step 4) in method and preparation condition, walk obtained presoma small particle in calcining ultra-thin
Acrylic/hydrotalcite-like nano piece, obtains layered bi-metal oxide adsorbent, is designated as LDOd。
Embodiment 5：
1) using embodiment 2 step 1) in method and preparation condition, prepared reverse micro emulsion A；
2) using embodiment 2 step 2) in method and preparation condition, prepared reverse micro emulsion B；
3) using embodiment 1 step 3) in method and preparation condition, reaction temperature is simply reduced to 25 DEG C, before obtaining
Drive the ultra-thin acrylic/hydrotalcite-like nano piece of body small particle.
4) using embodiment 1 step 4) in method and preparation condition, walk obtained presoma small particle in calcining ultra-thin
Acrylic/hydrotalcite-like nano piece, obtains layered bi-metal oxide adsorbent, is designated as LDOe。
Comparative example 1：
1) MgCl is weighed respectively2·6H2O and AlCl3·9H2O, adds deionized water, prepares total concentration of metal ions and is
0.45mol/L, MgCl2And AlCl3Molar concentration rate be 2：1, prepare solution A；
2) concentration is that 25% (w/w) ammoniacal liquor is solution B；
3) under the conditions of magnetic agitation, solution A and solution B are titrated simultaneously, pH is between 9.0~10.0 for control, room temperature
Stirring reaction 12h, afterwards the aging 24h under the conditions of 75 DEG C, gained slurries centrifuge 10min under 10000rpm rotating speeds, used successively
DMF, absolute ethyl alcohol and deionized water are washed 2 times respectively, are dried 12 hours under 60 DEG C of vacuum, are obtained LDH.
Comparative example 2：
According to step 1 in implementing 2)~method and condition 3), prepare the ultra-thin houghite of presoma small particle and receive
Rice piece, is designated as LDH-M.
Comparative example 3：
By the sample LDH of the gained of embodiment 2bStirring reaction 2 hours, the layered bi-metal being restored in deionized water
Hydroxide, is designated as LDHr。
Fig. 1 is embodiment 2, the XRD result figures of the gained sample of comparative example 1~3.LDH, LDH-M and LDH in figurerThree samples
Product occur in that three characteristic diffraction peaks of houghite 003,006 and 009 crystal face, wherein LDH-M and LDH at low 2 θrWith
LDH sample characteristics peak is compared, and its peak width substantially broadens, and intensity substantially dies down, and illustrates to be total to using of the present invention pair of microemulsion
Presoma LDH nanometer sheet crystallinity prepared by precipitation method method is relatively low, and its crystallinity becomes after bimetallic oxide hydration recovery
It is low.The d of three samples003Value is between 0.78~0.80nm, their cell parameter a and b (a=b=suitable with Cl-LDH
2d110) be aboutIt is consistent with literature value.The width and intensity of diffraction maximum reflect the crystallinity of sample well.In height
Three samples also all occur in that 110 and 113 diffraction maximums at 2 θ, it is apparent that LDH-M and LDHrCompared with LDH sample characteristics peak,
110 and 113 diffraction maximums are not only overlapping, and weakened, peak width broaden, and illustrate to be total to using of the present invention pair of microemulsion
Precipitation method method prepare presoma LDH nanometer sheets and as bimetallic oxide be hydrated recover obtained by LDH crystallinity it is relatively low,
And lamella is very thin.Layered bi-metal oxide is generated after when LDH-M is small through 500 DEG C of calcinings 5, XRD shows original
Rotating fields cave in, with reference to hydroxyl and the hydrone of interlayer lose, while occurring in that the diffraction maximum of new oxide phase.
Fig. 2 is embodiment 2, the N of the gained sample of comparative example 1 and 22Adsorption/desorption isotherms and graph of pore diameter distribution.Absorption etc.
Warm line shows that all samples are with H3- type hysteresis loops (P/P0>0.4) typical IV thermoisopleths, are shown to be mesoporous material
Material.Wherein the specific surface area of LDH-M samples is 140.83m2/ g, the LDH samples (53.28m prepared higher than traditional co-precipitation method2/
G), illustrating surfactant-free microemulsion coprecipitation can prepare that the big layered double hydroxide of specific surface area is ultra-thin to be received
Rice piece.And its calcined product LDObDue to losing the lamellar structure of original houghite, specific surface area has reduced, and is
113.05m2/ g, but the LDH samples prepared far above traditional co-precipitation method.LDH-M and LDObAperture be respectively 3.83 Hes
10.94nm, the LDH samples (21.87nm) prepared much smaller than traditional co-precipitation method, this explanation the first two sample lacks orderly piece
Rotating fields, concrete outcome is shown in Table 1.
Table 1：The BET of LDH nanometer sheets is than surface and aperture result
Fig. 3 is embodiment 2, the stereoscan photograph of the gained sample of comparative example 1~3.Electromicroscopic photograph is shown：Conventional coprecipitation
LDH samples prepared by method have obvious layer structure, and particle is larger and aggregation is obvious.And use of the present invention without surface-active
Agent microemulsion coprecipitation prepare presoma LDH-M particle diameters it is smaller, and because lamella is thin and presents bend it is dispersed.And it is forged
Burn product LDObBecause the lamellar structure of houghite is caved in, present and there is impalpable structure with little particle.Work as LDObIn water
After recovering in medium, due to LDH " memory effect ", LDHrThe lamellar structure of houghite is occurred in that again, and is still had
Good dispersiveness, but its lamella becomes big, and also lamella is also thickening, because in the process without microemulsion
The confinement effect of " washing basin " in system, acrylic/hydrotalcite-like nano piece can be with free growth.
Fig. 4 in the atomic force microscopy (a) and a figures of the gained sample of comparative example 3 along the cross section of red straight line point
Analyse (b).Atomic force microscopy shows prepared calcined product LDObAfter recovering in water, obvious aggregation is presented,
Although the crossed section analysis result of red straight line is shown, its particle size between 20~60nm, thickness is about 0.96~
3.22nm, but be apparent that other regions are presented and significantly build up, its particle diameter and thickness should be bigger, this and scanning electricity
Mirror result is consistent.
The application effect test example of embodiment 5
Subjects：Product made from embodiment 1-5, the products obtained therefrom of comparative example 1；
Test objective：Product and the gained LDH of comparative example 1 made from 1-5 of the embodiment of the present invention are investigated to low concentration in water body
The absorption property of phosphate radical.
Experiment packet：
Test 1 group：Product LDO made from embodiment 1a；
Test 2 groups：Product LDO made from embodiment 2b；
Test 3 groups：Product LDO made from embodiment 3c；
Test 4 groups：Product LDO made from embodiment 4d；
Test 5 groups：Product LDO made from embodiment 5e；
Contrast test group：Product LDH and LDH-M made from comparative example 1 and 2.
Test method：
Each 50mg of subjects of the present invention is added separately in the potassium dihydrogen phosphate aqueous solution that 50mL, concentration are 2mg/L,
Stirring reaction 5 hours.Every group of experiment is repeated six times, measures concentration after its processing, and determines its clearance, is averaged, wherein
The calculation formula of clearance is as follows：
Result of the test：
Table 2：The adsorption test result of product of the present invention and comparative sample to low phosphorus acid group in water body
| Group | Contrast groups | Contrast groups | Test 1 group | Test 2 groups | Test 3 groups | Test 4 groups | Test 5 groups |
| Test products | LDH | LDH-M | LDOa | LDOb | LDOc | LDOd | LDOe |
| Clearance (%) | 55.33 | 70.12* | 92.3*# | 92.6*# | 90.8*# | 91.8*# | 91.4*# |
Remarks：*Compared with contrast groups LDH, P<0.05；#Compared with contrast groups LDH-M, P<0.05.
Brief summary：It can be seen that by the result of the test of table 2：
As a result show：Under the conditions of identical mass adsorption agent is added, each experimental group of the invention (experiment 1,2,3,4 and 5 groups)
Compared with contrast groups LDH and LDH-M, their eliminating rate of absorption to low phosphorus acid group in water body all have significant difference,
It can be seen that present invention gained layered bi-metal oxide adsorbent LDO is obvious to the Adsorption effect of low phosphorus acid group in water body
Bulky grain houghite prepared by ultra-thin better than small particle LDH nanometer sheets and traditional co-precipitation method, this is primarily due to the present invention
The layered bi-metal oxide adsorbent LDO of gained forms LDO except being adsorbed using big specific surface area in structural remodeling
When, phosphate radical take part in the reconstruction of houghite, therefore they and the ultra-thin LDH nanometer sheets of small particle and conventional coprecipitation legal system
Standby bulky grain houghite is compared, and achieves unexpected technique effect.
Claims (3)
1. a kind of preparation method of layered bi-metal oxide adsorbent, it is characterised in that first using double microemulsion co-precipitation legal systems
Its standby presoma layered double hydroxide, then carries out high-temperature calcination to it again and prepares layered bi-metal oxide, specifically
Comprise the following steps：
1）MgCl is weighed respectively2·6H2O and AlCl3·9H2O, adds deionized water, prepare total concentration of metal ions for 0.05 ~
3.0 mol/L MgCl2And AlCl3Mixed-salt aqueous solution；N,N-dimethylformamide DMF is added into the mixing salt solution
With hydrophobic ionic liquid BmimPF6, wherein mixed-salt aqueous solution, DMF and BmimPF6Volume ratio be 2 ~ 15：30~50：40~
70, the min of magnetic agitation 30 ~ 60, treats that solution is changed into transparent from muddiness, has prepared reverse micro emulsion A at room temperature；
2）The ammoniacal liquor that certain volume concentration is 25% is taken, DMF and BmimPF is added thereto6, wherein 25% ammoniacal liquor, DMF and
BmimPF6Volume ratio be 2 ~ 15：30~50：40 ~ 70, the min of magnetic agitation 30 ~ 60, treats that solution is changed into from muddiness at room temperature
It is bright, prepare reverse micro emulsion B；
3）Under the conditions of magnetic agitation, reverse micro emulsion A and reverse micro emulsion B is titrated simultaneously, control pH 9.0 ~ 10.0 it
Between, 12 h of reaction are stirred at room temperature, afterwards the h of aging 10 ~ 24 under the conditions of 25 ~ 75 °C, gained slurries are in 10000 rpm rotating speeds
10 min of lower centrifugation, are washed 2 times respectively with DMF, absolute ethyl alcohol and deionized water successively, are dried 12 hours, are obtained under 60 °C of vacuum
The ultra-thin stratiform bimetallic oxide nanometer sheet of presoma small particle；
4）By step 3）The ultra-thin stratiform duplex metal hydroxide nanometer piece dry powder of presoma small particle of gained is put into Muffle furnace,
Calcined 3 ~ 8 hours under the conditions of 500 DEG C in air atmosphere, obtain layered bi-metal oxide adsorbent；
The preparation method of layered bimetallic oxide adsorbent, wherein step 1）Middle MgCl2And AlCl3Mol ratio be 2：
1；The aqueous solution in the reverse micro emulsion B that the aqueous phase is the reverse micro emulsion A of mixed-salt aqueous solution and aqueous phase is ammonia spirit,
DMF and BmimPF6Volume ratio it is essentially equal；Step 3）The ultra-thin layered double hydroxide of presoma small particle of gained is received
The lateral dimension of rice piece is 10 ~ 35 nm, and average thickness is 0.71 nm, is made up of individual layer layered double hydroxide piece；
The layered bi-metal oxide specific surface area that this method is prepared is 107.36 ~ 158.46 m2/ g, aperture be 8.56 ~
11.17 nm, pore volume is 0.358 ~ 0.468 cm3/g；
The layered bi-metal oxide adsorbent as made from the preparation method of layered bimetallic oxide adsorbent, is situated between in water
It is that 150 ~ 200 nm, thickness are that the homogeneous layered double hydroxide of 5 nm, particle diameter distribution is received that particle diameter can be recovered to be formed in matter
Rice piece.
2. layered bi-metal oxide adsorbent according to claim 1, it is characterised in that gained adsorbent is suitable for water
The adsorption applications of phosphate radical in body.
3. adsorbent according to claim 2 is suitable for the adsorption applications of phosphate radical in water body, it is characterised in that in water body
Phosphate concentration be 2 mg/L.
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| CN106241893A (en) * | 2015-06-06 | 2016-12-21 | 青岛科技大学 | A kind of flower ball-shaped nickel aluminum layered double hydroxide and its preparation method and application |
| CN107552007B (en) * | 2017-10-18 | 2019-05-10 | 福州大学 | Ion liquid modified magnalium laminar double-hydroxide adsorbent and its preparation and application |
| CN110105865A (en) * | 2019-05-30 | 2019-08-09 | 江苏美乔科技有限公司 | A kind of environment protection damp-proof UV oil polish and preparation method thereof |
| CN110372022B (en) * | 2019-06-26 | 2021-10-19 | 河海大学 | One-step synthesis method of macroscopic 3D multi-stage porous nano material |
| CN111426736B (en) * | 2020-05-27 | 2022-09-09 | 青岛科技大学 | Preparation method of CoAl-LDH/PANI modified electrode |
| CN112237897B (en) * | 2020-09-04 | 2022-02-08 | 南京大学 | Layered double-metal-based nano lanthanum material and preparation method and application thereof |
| CN112121758A (en) * | 2020-09-14 | 2020-12-25 | 江苏开放大学（江苏城市职业学院） | Layered double hydroxide composite attapulgite clay and preparation method thereof |
| CN113083216B (en) * | 2021-04-23 | 2023-11-10 | 江苏大学 | Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application of adsorbent in removing phosphate radical |
| CN113788502B (en) * | 2021-08-17 | 2023-02-17 | 天津大学 | Material preparation and detection method for distinguishing phosphate ion concentration in water environment |
| CN115646429A (en) * | 2022-10-27 | 2023-01-31 | 南京工业大学 | Ultrathin magnesium-lanthanum layered bimetallic oxide adsorbent and preparation method and application thereof |
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| JP4189492B2 (en) * | 2004-03-22 | 2008-12-03 | 独立行政法人物質・材料研究機構 | Layered double hydroxide / zeolite composite |
| JP5463525B2 (en) * | 2008-01-31 | 2014-04-09 | 独立行政法人産業技術総合研究所 | Selective adsorbent and method for producing the same |
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