CN106495200B - A kind of anhydrous slufuric acid salt form rare earth layered hydroxide and preparation method thereof - Google Patents
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide and preparation method thereof Download PDFInfo
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Abstract
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide and preparation method thereof, the anhydrous slufuric acid salt form rare earth layered hydroxide, chemical formula RE2(OH)4SO4, structural formula RE4(OH)8(SO4)2, it is powdered substance；RE is Eu~Lu, one kind in Y element；Preparation method is that ammonium sulfate is dissolved in into RE (NO3)3In solution, stirring forms homogeneous solution, and ammoniacal liquor is added into homogeneous solution, and it is 7.0~10.0 to continue stirring and adjusting pH value of solution, obtains suspension；By suspension hydro-thermal reaction, hydro-thermal compound is obtained；By hydro-thermal compound, room temperature is cooled to, obtains cooled product；Cooled product is centrifuged, cleaned with drying, obtains anhydrous slufuric acid salt form rare earth layered hydroxide.Technical scheme is simple and easy, RE/S mol ratios and two class important compound RE in obtained novel anhydrous sulfate type rare earth layered hydroxide2O2S and RE2O2SO4It is completely the same, it is to calcine the two classes laminarization and the preferable presoma of thing.
Description
Technical field：
The invention belongs to materials science field, and in particular to a kind of anhydrous slufuric acid salt form rare earth layered hydroxide and
Its preparation method.
Background technology：
Rare earth layered hydroxide (Layered rare-earth hydroxide, LREH) sensing, medicament transport, in
Son capture treatment and the field such as luminous are got the attention, and its formula is RE2(OH)6-m(Ax-)m/x·nH2O (1≤m≤2, An-
For the anion of n valencys).It is two major classes that can be divided to LREH according to its chemical composition and structure feature, i.e. RE2(OH)5(Ax-)1/x·
nH2O (m=1, A=Cl-、NO3 -、SO4 2-Deng) and RE2(OH)4(Ax-)2/x·nH2O (m=2, A=SO4 2-Deng).It is relevant at present dilute
The research of native layered hydroxide focuses primarily upon the first kind (m=1), including its synthesis, architectural feature, stripping, self assembly and
Light functionalization etc..Research about the second class (m=2) rare earth lamellar compound is then extremely limited, until just having research in 2010
Personnel have been synthesized first using rare earth sulfate and the ammonium of hexa-methylene four as raw material, using sluggish precipitation belongs to such sulfate
Type lamellar compound RE2(OH)4SO4·nH2O (RE=Pr~Tb, n=2~2.3).The unique stoicheiometry of such compound makes
It, which turns into, prepares rare-earth oxide sulfate (RE2O2) and rare earth oxysulfate (RE S2O2SO4) two class important compounds ideal before
Drive body.RE2(OH)4SO4·nH2O (RE-241) is the sulfate type rare earth stratiform hydroxide that currently the only one kind has been reported
Thing.Due to the violent hydrolysis of some minor radius heavy rare earth elements in the solution, cause RE3+/OH-、RE3+/SO4 2-And SO4 2-/OH-
Mol ratio deviate RE2(OH)4SO4·nH2Ratio in O, cause the conjunction of such compound of some minor radius heavy rare earth elements
Into can not realize, its element species be only limitted to LREE (La~Eu) and the larger heavy rare earth element of some radiuses (Gd and
Tb).It is limited to RE2(OH)4SO4·nH2O element species, it is only capable of calcining out some rare earth elements at present as presoma
Oxysulfate and oxysulfide.Because the crystallization water is directly coordinated with rare earth ion in such compound, therefore whether go out in structure
The existing crystallization water directly affects the crystal structure feature of product and the coordination mode of the coordination polyhedrom centered on rare earth ion.
The common method of synthesizing rare-earth layered hydroxide is the precipitation method and hydro-thermal method.The precipitation method are often sub- with precipitating reagent such as six
Tetramine (HMT, (CH2)6N4) have hydrolysis at room temperature slowly, under high temperature in air easily generation formaldehyde and its derivative and
The shortcomings of reducing precipitation reaction yield.It is obvious excellent that hydro-thermal method has that product purity height, good dispersion, crystallinity are high, pollution is small etc.
Gesture, and can realize having to product thing phase and pattern etc. by adjusting the parameters such as hydrothermal temperature, time and pH value of reaction system
Effect control.The current synthetic method about the second class sulfate type lamellar compound is limited primarily to the precipitation method.
The content of the invention：
The purpose of the present invention is to be directed to Problems Existing, there is provided a kind of anhydrous slufuric acid salt form rare earth layered hydroxide and its system
Preparation Method.Purpose is to enrich existing rare earth lamellar compound species, and realizes the anhydrous slufuric acid salt form rare earth layer of heavy rare earth element
The synthesis of shape hydroxide, preferable precursor is provided for the preparation of rare earth oxysulfate and rare-earth oxide sulfate.
To achieve the above object, the present invention uses following technical scheme：
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are RE2(OH)4SO4, structural formula RE4(OH)8
(SO4)2, in the anhydrous slufuric acid salt form rare earth layered hydroxide structure, RE3+Nine coordination polyhedroms are formed with hydroxyl, sulfate radical
REO9, wherein RE is one kind in Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Y element.
Nine described coordination polyhedrom REO9For three cap triangular prisms, six of which oxygen comes from oh group and the other three
Oxygen comes from sulfate radical.
In described anhydrous slufuric acid salt form rare earth layered hydroxide structure, by nine coordination polyhedrom REO9With coplanar and common
The mode on side is built to form main stor(e)y plate, and main stor(e)y plate is connected by playing the sulfate radical of electric charge balanced action in interlayer.
Wherein：
When RE is Eu elements, anhydrous slufuric acid salt form rare earth layered hydroxide shape is defined hexagon micron plate, and thickness is
0.5~0.8 μm, a length of 4~8 μm；
When RE is Gd elements, anhydrous slufuric acid salt form rare earth layered hydroxide shape is defined hexagon micron plate, and thickness is
0.5~0.8 μm, a length of 4~8 μm；
When RE is Tb elements, anhydrous slufuric acid salt form rare earth layered hydroxide shape is defined hexagon micron plate, thickness 1
~3 μm, a length of 15~20 μm；
When RE is Dy elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as spherical aggregate, and a diameter of 60
~110 μm；
When RE is Ho elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as reunion ball；A diameter of 60~100 μ
m；
When RE is Er elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as submillimeter reunion ball, and a diameter of 100
~250 μm；
When RE is Tm elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as spherical aggregate, and a diameter of 80
~150 μm；
When RE is Yb elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as irregular pattern aggregate, diameter
For 120~220 μm；
When RE is Lu elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as the spherical aggregate of submillimeter,
A diameter of 150~200 μm；
When RE is Y element, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as submillimeter reunion ball, and a diameter of 120
~200 μm.
A kind of preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide, comprises the following steps：
(1) ammonium sulfate is dissolved in RE (NO3)3In solution, stirring forms homogeneous solution, and ammonia is added into homogeneous solution
Water, and continue to stir, regulation pH value of solution is 7.0~10.0, obtains suspension；Wherein, RE Eu, Gd, Tb, Dy, Ho, Er, Tm,
One kind in Yb, Lu or Y element, ammonium sulfate and RE (NO3)3The addition of solution in molar ratio, SO4 2-：RE3+=0.5~
5；
(2) by suspension, hydro-thermal reaction is carried out, obtains hydro-thermal compound；Wherein, hydrothermal temperature is 150~200
DEG C, the hydro-thermal reaction time is 1~72h；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is subjected to eccentric cleaning, centrifugation and drying, obtains anhydrous slufuric acid salt form rare earth stratiform hydrogen-oxygen
Compound RE2(OH)4SO4。
In described step (1), RE (NO3)3The concentration of solution is 0.05~0.5mol/L.
In described step (1), the mixing time for forming homogeneous solution is 10~20min.
In described step (1), ammoniacal liquor feed postition is to be added dropwise.
In described step (1), ammoniacal liquor is added, the time persistently stirred is 10~20min.
In described step (2), hydro-thermal reaction is carried out in a kettle.
In described step (4), the eccentric cleaning process of cooled product is：First use distilled water eccentric cleaning, then with anhydrous
Ethanol eccentric cleaning, wherein, distilled water eccentric cleaning number is 3 times, and absolute ethyl alcohol eccentric cleaning number is 1 time.
In described step (4), drying temperature is 50~80 DEG C.
It is main in the preparation process of anhydrous slufuric acid salt form rare earth layered hydroxide that following react occurs：
2RE(NO3)3+(NH4)2SO4+4NH3·H2O→RE2(OH)4SO4+6NH4NO3
Beneficial effects of the present invention：
(1) present invention provides a kind of anhydrous slufuric acid salt form rare earth stratiform hydrogen-oxygen with new chemical the Nomenclature Composition and Structure of Complexes feature
Compound RE2(OH)4SO4Hydrothermal preparing process.Rare earth ion (RE3+) in aqueous by hydration and hydrolysis, formed multiple
Close ion [RE (OH)x(H2O)y]3-x, x+y=6, RE=Eu~Lu, containing Y), by modulating pH value in reaction and temperature adjustment rare earth
The hydrolysis of ion, such compound is set to extend to the minimum heavy rare earth Lu of ionic radius.
(2) technical scheme is simple and easy, obtained novel anhydrous sulfate type layered hydroxide RE2(OH)4SO4Middle RE/S mol ratios and two class important compound RE2O2S and RE2O2SO4It is completely the same, it is to calcine the two classes lamellar compound
Preferable presoma.
(3) the use of gentle ammonium sulfate is sulphur source in preparation process using the method for the present invention, safety non-pollution, formation
Product crystallinity it is high, by modulate hydro-thermal reaction parameter can Effective Regulation compound microscopic appearance.
Brief description of the drawings：
Fig. 1 is Eu prepared by the embodiment of the present invention 12(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Fig. 2 is Gd prepared by the embodiment of the present invention 22(OH)4SO4Diffraction maximum indexation XRD spectrum (a, λ=
0.15406nm)
And its SEM shape appearance figures (b)；
Fig. 3 is Tb prepared by the embodiment of the present invention 32(OH)4SO4XRD spectrum (a) and SEM patterns (b)；
Fig. 4 is Dy prepared by the embodiment of the present invention 42(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Fig. 5 is Ho prepared by the embodiment of the present invention 52(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Fig. 6 is Y prepared by the embodiment of the present invention 62(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Fig. 7 is Er prepared by the embodiment of the present invention 72(OH)4SO4XRD spectrum (a), FTIR collection of illustrative plates (b) and SEM shape appearance figures
(c)；
Fig. 8 is Tm prepared by the embodiment of the present invention 82(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Fig. 9 is Yb prepared by the embodiment of the present invention 92(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Figure 10 is Lu prepared by the embodiment of the present invention 102(OH)4SO4XRD spectrum (a) and SEM shape appearance figures (b)；
Figure 11 is RE prepared by the embodiment of the present invention 1~102(OH)4SO4Layered crystal structure schematic diagram.
Embodiment：
With reference to embodiment, the present invention is described in further detail.
Chemical reagent employed in present example is the pure level product of analysis；
The embodiment of the present invention carries out XRD points using the RINT2200V/PC types x-ray diffractometer of Japanese Rigaku companies
Analysis；Using S-5000 types field emission scanning electron microscope (FE-SEM) observing samples pattern of Japanese Hitachi companies；Using
The infrared spectrum of 4200 type FT-IR spectrophotometer products of JASCO companies；Using Japanese Nippon Jarrell-Ash companies
IRIS Advantage type icp analysis instrument determination samples RE and N content (analysis precision：0.01wt%)；Using the U.S.
CS-444LS types carbon/sulphur of LECO companies is the same as the S and C content (analysis precision for determining instrument detection sample：0.01wt%).
Hydrothermal reaction kettle inner bag material is polytetrafluoroethylene (PTFE), specification 100ml, and steel bushing material is stainless steel, and baking oven is electronics
Temperature control oven, the temperature difference are less than 1 DEG C；
The structure of lamellar compound is parsed using TOPAS softwares in the present invention, for needing to carry out structure elucidation
Sample XRD data are obtained using step-by-step movement scanning, step-length used is 0.02 °, residence time for often walking is 35s.
It is the preferred embodiment of the present invention below.
Embodiment 1
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Eu2(OH)4SO4, structural formula Eu4(OH)8
(SO4)2, shape is defined hexagon micron plate, and thickness is 0.5~0.8 μm, a length of 4~8 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Eu2(OH)4SO4Preparation method, comprise the following steps：
(1) Eu (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Eu
(NO3)3In solution, ammonium sulfate and Eu (NO3)3The addition of solution in molar ratio, SO4 2-：Eu3+=1：1,10min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 10min, regulation pH value of solution is 10.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
1h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Eu2(OH)4SO4, its XRD,
As shown in Fig. 1 (a)；SEM schemes, and as shown in Fig. 1 (b), its shape is defined hexagon micron plate, and thickness is 0.5~0.8 μm, and a length of 4
~8 μm；Gained Eu is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram it is as shown in figure 11.
Embodiment 2
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Gd2(OH)4SO4, structural formula Gd4(OH)8
(SO4)2, shape is defined hexagon micron plate, and thickness is 0.5~0.8 μm, a length of 4~8 μm.
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide Gd2(OH)4SO4Preparation method, comprise the following steps：
(1) Gd (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Gd
(NO3)3In solution, ammonium sulfate and Gd (NO3)3The addition of solution in molar ratio, SO4 2-：Gd3+=1：1,10min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 10min, regulation pH value of solution is 10.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Gd2(OH)4SO4, its basis
The XRD of Rietveld analysis result indexation, as shown in Fig. 2 (a), elementary analysis (ICP) shows that its chemical composition is Gd2
(OH)3.91(SO4)1.01(NO3)0.003(CO3)0.02, the wherein NO of denier3 -Come from adsorption and CO3 2-Come from alkaline reaction
CO in the air that liquid (pH=10) is dissolved2；SEM schemes, and as shown in Fig. 2 (b), its pattern is defined hexagon micron plate, thickness
For 0.5~0.8 μm, a length of 4~8 μm；Gained Gd is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram as scheme
Shown in 11.
Embodiment 3
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Tb2(OH)4SO4, structural formula Tb4(OH)8
(SO4)2, shape is defined hexagon micron plate, and thickness is 1~3 μm, a length of 15~20 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Tb2(OH)4SO4Preparation method, comprise the following steps：
(1) Tb (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；4g ammonium sulfates are dissolved in Tb
(NO3)3In solution, ammonium sulfate and Tb (NO3)3The addition of solution in molar ratio, SO4 2-：Tb3+=5：1,10min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 10min, regulation pH value of solution is 9.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
72h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Tb2(OH)4SO4, its XRD,
As shown in Fig. 3 (a)；SEM schemes, and as shown in Fig. 3 (b), its shape is defined hexagon micron plate, and thickness is 1~3 μm, a length of 15~
20μm；Gained Tb is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram it is as shown in figure 11.
Embodiment 4
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Dy2(OH)4SO4, structural formula Dy4(OH)8
(SO4)2, it is shaped as spherical aggregate, a diameter of 60~110 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Dy2(OH)4SO4Preparation method, comprise the following steps：
(1) Dy (NO that concentration is 0.5mol/L are taken3)3Solution, its volume are 60ml；4g ammonium sulfates are dissolved in Dy
(NO3)3In solution, ammonium sulfate and Dy (NO3)3The addition of solution in molar ratio, SO4 2-：Dy3+=1：1,10min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 10min, regulation pH value of solution is 8.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Dy2(OH)4SO4, its XRD,
As shown in Fig. 4 (a), as can be seen from the figure products therefrom is pure phase；SEM schemes, and as shown in Fig. 4 (b), it is shaped as spherical group
Aggressiveness, a diameter of 60-110 μm；Gained Dy is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram such as Figure 11 institutes
Show.
Embodiment 5
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Ho2(OH)4SO4, structural formula Ho4(OH)8
(SO4)2, it is shaped as reunion ball；A diameter of 60~100 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Ho2(OH)4SO4Preparation method, comprise the following steps：
(1) Ho (NO that concentration is 0.05mol/L are taken3)3Solution, its volume are 60ml；0.2g ammonium sulfates are dissolved in Ho
(NO3)3In solution, ammonium sulfate and Ho (NO3)3The addition of solution in molar ratio, SO4 2-：Ho3+=1：2,15min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 15min, regulation pH value of solution is 7.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 50 DEG C, obtains product Ho2(OH)4SO4, its XRD,
As shown in Fig. 5 (a), as can be seen from the figure products therefrom is pure phase；Elementary analysis (ICP) shows that its chemical composition is Ho2
(OH)4.01(SO4)0.98(NO3)0.01(CO3)0.01, the wherein NO of denier3 -Come from adsorption and CO3 2-It is molten to come from reaction solution institute
CO in the air of solution2；SEM schemes, and as shown in Fig. 5 (b), it is shaped as reunion ball, a diameter of 60-100 μm；Solved through Rietveld
Analysis gained Ho2(OH)4SO4Layered crystal structure schematic diagram it is as shown in figure 11.
Embodiment 6
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Y2(OH)4SO4, structural formula Y4(OH)8
(SO4)2, it is shaped as submillimeter reunion ball, a diameter of 120~200 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Y2(OH)4SO4Preparation method, comprise the following steps：
(1) Y (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Y
(NO3)3In solution, ammonium sulfate and Y (NO3)3The addition of solution in molar ratio, SO4 2-：Y3+=1：1, stir 15min, shape
Into homogeneous solution, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 15min, regulation pH value of solution is 7.0, is obtained suspended
Liquid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Y2(OH)4SO4, its XRD, such as
Shown in Fig. 6 (a), as can be seen from the figure products therefrom is pure phase；Elementary analysis (ICP) shows that its chemical composition is Y2
(OH)3.918(SO4)1.03(NO3)0.002(CO3)0.01, the wherein NO of denier3 -Come from adsorption and CO3 2-Come from reaction solution institute
CO in the air of dissolving2；SEM schemes, and as shown in Fig. 6 (b), it is shaped as submillimeter reunion ball, a diameter of 120-200 μm；Through
Rietveld parsing gained Y2(OH)4SO4Layered crystal structure schematic diagram it is as shown in figure 11.
Embodiment 7
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Er2(OH)4SO4, structural formula Er4(OH)8
(SO4)2, it is shaped as submillimeter reunion ball, a diameter of 100~250 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Er2(OH)4SO4Preparation method, comprise the following steps：
(1) Er (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Er
(NO3)3In solution, ammonium sulfate and Er (NO3)3The addition of solution in molar ratio, SO4 2-：Er3+=1：1,20min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 20min, regulation pH value of solution is 7.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 150 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Er2(OH)4SO4, its XRD,
As shown in Fig. 7 (a), as can be seen from the figure products therefrom is pure phase.Its infared spectrum is shown in Fig. 7 (b), and its infrared behavior enters one
Step proves that such compound is free of the crystallization water；SEM schemes, and as shown in Fig. 7 (b), it is shaped as submillimeter reunion ball, a diameter of 100-
250μm；Gained Er is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram it is as shown in figure 11.
Embodiment 8
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Tm2(OH)4SO4, structural formula Tm4(OH)8
(SO4)2, it is shaped as spherical aggregate, a diameter of 80~150 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Tm2(OH)4SO4Preparation method, comprise the following steps：
(1) Tm (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Tm
(NO3)3In solution, ammonium sulfate and Tm (NO3)3The addition of solution in molar ratio, SO4 2-：Tm3+=1：1,20min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 20min, regulation pH value of solution is 7.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Tm2(OH)4SO4, its XRD,
As shown in Fig. 8 (a), as can be seen from the figure products therefrom is pure phase；SEM schemes, and as shown in Fig. 8 (b), it is shaped as spherical group
Aggressiveness, a diameter of 80-150 μm；Gained Tm is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram such as Figure 11 institutes
Show.
Embodiment 9
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Yb2(OH)4SO4, structural formula Yb4(OH)8
(SO4)2, it is shaped as irregular pattern aggregate, a diameter of 120~220 μm.
Anhydrous slufuric acid salt form rare earth layered hydroxide Yb2(OH)4SO4Preparation method, comprise the following steps：
(1) Yb (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Yb
(NO3)3In solution, ammonium sulfate and Yb (NO3)3The addition of solution in molar ratio, SO4 2-：Yb3+=1：1,20min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 20min, regulation pH value of solution is 7.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 80 DEG C, obtains product Yb2(OH)4SO4, its XRD,
As shown in Fig. 9 (a), as can be seen from the figure products therefrom is pure phase；SEM schemes, and such as shown in 9 (b), it is shaped as irregular shape
Aggregate, a diameter of 120-220 μm；Gained Yb is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram such as Figure 11
It is shown.
Embodiment 10
A kind of anhydrous slufuric acid salt form rare earth layered hydroxide, its chemical formula are Lu2(OH)4SO4, structural formula Lu4(OH)8
(SO4)2, it is shaped as the spherical aggregate of submillimeter, a diameter of 150~200 μm.
The preparation method of the anhydrous slufuric acid salt form rare earth layered hydroxide, comprises the following steps：
(1) Lu (NO that concentration is 0.1mol/L are taken3)3Solution, its volume are 60ml；0.8g ammonium sulfates are dissolved in Lu
(NO3)3In solution, ammonium sulfate and Lu (NO3)3The addition of solution in molar ratio, SO4 2-：Lu3+=1：1,20min is stirred,
Homogeneous solution is formed, ammoniacal liquor is added dropwise into homogeneous solution, and continues to stir 20min, regulation pH value of solution is 7.0, is hanged
Turbid；
(2) by suspension, hydro-thermal reaction is carried out in a kettle, and hydrothermal temperature is 200 DEG C, and the hydro-thermal reaction time is
24h, obtain hydro-thermal compound；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is carried out into eccentric cleaning, centrifugation and drying, eccentric cleaning process is：First with distilled water from
The heart cleans 3 times, then with absolute ethyl alcohol eccentric cleaning 1 time, drying temperature is 70 DEG C, obtains product Lu2(OH)4SO4, its XRD,
As shown in Figure 10 (a), as can be seen from the figure products therefrom is pure phase；Elementary analysis (ICP) shows that its chemical composition is Lu2
(OH)3.92(SO4)1.03(NO3)0.003(CO3)0.01, the wherein NO of denier3 -Come from adsorption and CO3 2-Come from reaction solution institute
CO in the air of dissolving2；SEM schemes, and as shown in Figure 10 (b), it is shaped as the spherical aggregate of submillimeter, a diameter of 150-
200μm；Gained Lu is parsed through Rietveld2(OH)4SO4Layered crystal structure schematic diagram it is as shown in figure 11.
Claims (6)
1. a kind of preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide, wherein, described anhydrous slufuric acid salt form rare earth
Layered hydroxide chemical formula is RE2(OH)4SO4, structural formula RE4(OH)8(SO4)2, anhydrous slufuric acid salt form rare earth stratiform hydrogen-oxygen
In compound structure, RE3+Nine coordination polyhedrom REO are formed with hydroxyl, sulfate radical9, RE Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
One kind in Lu or Y element, wherein：
Nine described coordination polyhedrom REO9For three cap triangular prisms, six of which oxygen comes from oh group and the other three oxygen comes
From sulfate radical；
In described anhydrous slufuric acid salt form rare earth layered hydroxide structure, by nine coordination polyhedrom REO9With coplanar and common side
Mode is built to form main stor(e)y plate, and main stor(e)y plate is connected by playing the sulfate radical of electric charge balanced action in interlayer；
When RE is Eu elements, anhydrous slufuric acid salt form rare earth layered hydroxide shape is defined hexagon micron plate, and thickness is 0.5~
0.8 μm, a length of 4~8 μm；
When RE is Gd elements, anhydrous slufuric acid salt form rare earth layered hydroxide shape is defined hexagon micron plate, and thickness is 0.5~
0.8 μm, a length of 4~8 μm；
When RE is Tb elements, anhydrous slufuric acid salt form rare earth layered hydroxide shape is defined hexagon micron plate, and thickness is 1~3 μ
M, a length of 15~20 μm；
When RE is Dy elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as spherical aggregate, and a diameter of 60~110
μm；
When RE is Ho elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as reunion ball；A diameter of 60~100 μm；
When RE is Er elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as submillimeter reunion ball, a diameter of 100~
250μm；
When RE is Tm elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as spherical aggregate, and a diameter of 80~150
μm；
When RE is Yb elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as irregular pattern aggregate, and a diameter of 120
~220 μm；
When RE is Lu elements, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as the spherical aggregate of submillimeter, diameter
For 150~200 μm；
When RE is Y element, anhydrous slufuric acid salt form rare earth layered hydroxide is shaped as submillimeter reunion ball, and a diameter of 120~200
μm；
Characterized in that, described preparation method comprises the following steps：
(1) ammonium sulfate is dissolved in RE (NO3)3In solution, stirring forms homogeneous solution, and ammoniacal liquor is added into homogeneous solution, and
Lasting stirring, regulation pH value of solution is 7.0~10.0, obtains suspension；Wherein, RE Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Or one kind in Y element, addition in molar ratio, SO4 2-：RE3+=0.5~5；
(2) by suspension, hydro-thermal reaction is carried out, obtains hydro-thermal compound；Wherein, hydrothermal temperature is 150~200 DEG C, water
The thermal response time is 1~72h；
(3) by hydro-thermal compound, room temperature is naturally cooled to, obtains cooled product；
(4) cooled product is subjected to eccentric cleaning, centrifugation and drying, obtains anhydrous slufuric acid salt form rare earth layered hydroxide
RE2(OH)4SO4。
2. the preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide according to claim 1, it is characterised in that institute
In the step of stating (1), RE (NO3)3The concentration of solution is 0.05~0.5mol/L.
3. the preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide according to claim 1, it is characterised in that institute
In the step of stating (1), ammoniacal liquor feed postition is to be added dropwise.
4. the preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide according to claim 1, it is characterised in that institute
In the step of stating (2), hydro-thermal reaction is carried out in a kettle.
5. the preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide according to claim 1, it is characterised in that institute
In the step of stating (4), the eccentric cleaning process of cooled product is：Distilled water eccentric cleaning is first used, then is centrifuged clearly with absolute ethyl alcohol
Wash, wherein, distilled water eccentric cleaning number is 3 times, and absolute ethyl alcohol eccentric cleaning number is 1 time.
6. the preparation method of anhydrous slufuric acid salt form rare earth layered hydroxide according to claim 1, it is characterised in that institute
In the step of stating (4), drying temperature is 50~80 DEG C.
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| CN109694046A (en) * | 2019-02-01 | 2019-04-30 | 渤海大学 | A method of rare earth orthophosphates is prepared using from sacrifice template |
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