CN101985106B - Preparation method and application of novel caesium-removing silver-tin selenide microporous material - Google Patents
Preparation method and application of novel caesium-removing silver-tin selenide microporous material Download PDFInfo
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- CN101985106B CN101985106B CN2009101122768A CN200910112276A CN101985106B CN 101985106 B CN101985106 B CN 101985106B CN 2009101122768 A CN2009101122768 A CN 2009101122768A CN 200910112276 A CN200910112276 A CN 200910112276A CN 101985106 B CN101985106 B CN 101985106B
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- ion
- yin
- exchange
- selenides
- exchange performance
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Abstract
The present invention relates to a kind of Yin-tin selenides poromerics preparation methods and its ion-exchange performance application. The compound is synthesized using simple solvent thermal process, and chemical formula is [(Me) 2NH2] 0.75Ag1.25SnSe3, and molecular weight 524.75 belongs to tetragonal crystal system, space group P-421m, and cell parameter is
α=β=γ=90 °,
Z=2. Its structure is the open-framework with 3 D pore canal, the compound has excellent ion-exchange performance to alkali metal Cs+, Rb+ ion in aqueous solution, especially under condition of different pH, including all having strong ion-exchange capacity and single selective under highly acid and strong alkali environment to Cs+ ion, thus Yin prepared by the present invention-tin selenides poromerics can be used for excluding radioactive element caesium from high activity liquid waste.
Description
Technical field
The present invention relates to preparation method and the ion-exchange performance application thereof of a class Yin-Xi selenides poromerics.This compound in the aqueous solution to alkali metal Cs
+, Rb
+Ion has good ion-exchange performance, especially to Cs
+Ion shows as under condition of different pH, and comprise under highly acid and strong alkali environment strong ion-exchange capacity and high selective is arranged, thereby significant for get rid of the radioactive element caesium from high activity liquid waste.
Background technology
Metal chalcogenide with open-framework structure can cause people's broad interest with semiconductor light electrical property and porous perfect adaptation because of it.This compounds has wide application prospects at aspects such as catalysis, absorption, separation, fast-ionic conductor, ion-exchanges.Compare with traditional oxygen containing class zeolitic material, the chalcogen in metal chalcogen poromerics is for some heavy metal (pb
2+, Cd
2+, Hg
2+) and weight alkali metal (Rb
+, Cs
+), alkaline-earth metal (Sr
2+) stronger affinity is arranged, thereby be the ion exchange material that a class has DEVELOPMENT PROSPECT very much.Since the pioneering research work on the metal chalcogenide ion-exchange performance, synthetic metal chalcogenide with high selectivity ion-exchange performance has become one of pursuing a goal of people since people such as Kanatzidis.This compounds is having actual using value aspect the purifying of environmental improvement and drinking water.
Society, people are faced with increasing energy problem, and national governments are all making great efforts the exploitation nuclear energy technology, however the waste liquid that processing nuclear energy produces is a large technical barrier.Many radionuclides may be transformed in our food and occur concentratedly in water body or soil, environment is had very large harm.In high activity liquid waste
137Cs is one of main heat release product, and its shared radioactivity share is larger.Become middle low radioactive waste liquid to high activity liquid waste, in acid medium, the removal of caesium is a very important step.The method of separating caesium from high activity liquid waste mainly contains precipitation, volatilization, solvent extraction and ion-exchange etc.The precipitation method are early used, but because of it Separation of Solid and Liquid operating difficulties under the hot condition, belong to again intermittent operation, thereby limited its application; Volatility process operates usually under high temperature, high radioactivity condition, thus to experimental facilities require highly, the security of method is not good, is difficult to really apply.Solvent extraction is easily realized the continuous and automatic operation, is suitable for using under the hot condition, but is difficult to find suitable extractant.Inorganic ion exchange material has become one of means comparatively economic and suitable in the nuclear waste processing with its peculiar advantage.Inorganic ions exchange commonly used comprises zeolite, polyvalent metal phosphate, heteropolyacid salt and compound ion exchange material thereof, insoluble ferrocyanide, titanium-silicon compound etc., and for the ion exchange material research of chalcogenide or at the early-stage.With respect to other ion-exchangers such as zeolites, chalcogenide ion exchange material or rarely found.That has reported has [(a CH
3CH
2CH
2)
2NH
2]
5In
5Sb
6S
191.45H
2O, K
6Sn[Zn
4Sn
4S
17], (NH
4)
4In
12Se
20Deng.Our seminar synthesized an example to cesium ion have high selective and exchange capacity germanium-antimony-sulphur compound [(Me)
2NH
2]
2Sb
2GeS
6Kanatzidis and partner thereof have developed the chalcogenide K of a routine layer structure
1.9Mn
0.95Sn
2.05S
6, ion-exchange performance research shows that this compound is to caesium, strontium and some heavy metal ion pb
2+, Cd
2+, Hg
2+Good switching performance is arranged.Yet cesium ion is had single-minded optionally metal chalcogenide yet there are no report.
Summary of the invention
The present invention has prepared different metal chalcogenides that an example has a three-dimensional open-framework [(Me) by solvent thermal reaction
2NH
2]
0.75Ag
1.25SnSe
3.Ion-exchange performance research show this compound in the aqueous solution to alkali metal Cs
+, Rb
+Ion has good ion-exchange performance, especially to Cs
+Ion has strong ion-exchange capacity and high selective.
[(Me)
2NH
2]
0.75Ag
1.25SnSe
3Synthesize by solvent-thermal method: with a certain amount of AgCl, after weighing up respectively, Sn, Se powder sample join the N of 5mL, in the hydrazine hydrate of N '-solvent dimethylformamide and 1mL (80%) mixed solvent, room temperature fully stirs in the 28mL stainless steel cauldron that rear inclosure liner is polytetrafluoroethylene (PTFE), can obtain peony bulk crystals (target product) after a couple of days in 160 ℃ of solvent thermal reactions, and the minute quantity black impurity, the crystalline product productive rate is 62%.Solvent N in this solvent thermal reaction, N '-dimethyl formamide is hydrolyzed, and original position has generated protonated dimethylamine and has entered into compound [(Me)
2NH
2]
0.75Ag
1.25SnSe
3Structure in.
The Yin of microcellular structure-the Xi selenides [(Me)
2NH
2]
0.75Ag
1.25SnSe
3Molecular weight is 524.75, belongs to tetragonal crystal system, and space group is P-42
1M, cell parameter is
α=β=γ=90 °,
Z=2.Its structure is the open-framework with 3 D pore canal.At c-axis direction [Ag
4Se
8] bunch by the silver atoms of tetrahedral coordination, connect to be formed [Ag
5Se
8] one-dimensional chain; Along ab plane, [Ag
5Se
8] one-dimensional chain is further by [Sn
2Se
2] forming three-dimensional net structure, generated in-situ dimethylamine cation is filled in 3 D pore canal, and direction has approximately along [0,0,1]
Duct, the duct size of other both directions [1,1,0] and [1 ,-1,0] is
The porosity of calculate finding to remove after dimethylamine by the PLATON program is approximately 35%.
Single ionic exchange test research shows that compound is in each alkali metal ion aqueous solution of same isoconcentration (0.5mmol/L), [(Me)
2NH
2]
0.75Ag
1.25SnSe
3Ion exchange ratio is respectively: Cs
+87%, Rb
+84%.Ion-exchange can not occur in otheralkali metal.In the selective ion exchange experiment, work as Cs
+: the Rb ion concentration is 1: 1 o'clock, and after ion-exchange, the elementary analysis test shows only Cs
+Exchanged entering in compound.The change condition, work as Cs
+: Rb
+Ion concentration is 1: 10 o'clock, and after ion-exchange, the elementary analysis test shows to only have Cs
+Exchanged entering in compound, visible compound is to Cs
+Strong ion-exchange capacity and single-minded selective is arranged.This is significant for removing the radioactive element caesium in nuclear waste, has developed a kind of ion-exchanger of new processing nuclear waste.
The solid ultraviolet-visible absorption spectroscopy band gap of compound is respectively 1.88eV, Cs
+, Rb
+Its band gap of product after ion-exchange is respectively 1.74,1.77eV, and after ion-exchange, trickle red shift has occurred its band gap magnitude.
Description of drawings
Fig. 1. Yin-the Xi selenides [(Me)
2NH
2]
0.75Ag
1.25SnSe
3Tomograph.
Fig. 2. Yin-the Xi selenides [(Me)
2NH
2]
0.75Ag
1.25SnSe
3The ion-exchange product tomograph.
Fig. 3. Yin-the Xi selenides [(Me)
2NH
2]
0.75Ag
1.25SnSe
3And the pure phase X-ray powder diffraction pattern of ion-exchange product, wherein: a: compound is [(Me)
2NH
2]
0.75Ag
1.25SnSe
3Monocrystalline simulation coatings, b: compound [(Me)
2NH
2]
0.75Ag
1.25SnSe
3The experiment test coatings, c:Cs-ion exchange product monocrystalline simulation coatings, d:Cs-ion exchange product experiment test coatings, e:Rb-ion exchange product monocrystalline simulation coatings, f:Rb-ion exchange product experiment test coatings.
The specific embodiment
Embodiment 1: Yin-the Xi selenides [(Me)
2NH
2]
0.75Ag
1.25SnSe
3Preparation
With AgCl (1.0mmol, 0.145g), Sn (1.0mmol, 0.114g), Se (3mmol, 0.237g) joining the N of 5mL, in N '-solvent dimethylformamide, room temperature fully stirs in the 28mL stainless steel cauldron that rear inclosure liner is polytetrafluoroethylene (PTFE), in 160 ℃ of isothermal reactions 7 days, then naturally be cooled to room temperature, filter and with ethanol, fully wash and can obtain peony bulk crystals (target product) and a small amount of black powder, the crystalline product productive rate can reach 62%.Initial reactant is amplified 5 times react also and can obtain identical result, show that this compound can preparation in macroscopic quantity, this is very important for practical application.
Embodiment 2: Yin-the Xi selenides [(Me)
2NH
2]
0.75A
G1.25SnSe
3To alkali-metal ion-exchange experiment
A typical ion-exchange experiment: alkali metal chloride ACl (A=Rb, Cs) (2mmol) is dissolved in respectively in the distilled water of 20mL, then adds 100mg[(Me)
2NH
2]
0.75A
G1.25SnSe
3Crystal prototype, mixture at room temperature stirred 12 hours, and the ion-exchange product filters and, with distilled water, ethanol and ether fully washing successively, can obtain the product of alkali metal ion exchange afterwards.
Claims (3)
1. have that ion-exchange performance Yin-the Xi selenides [(Me)
2NH
2]
0.75Ag
1.25SnSe
3, molecular weight is 524.75, belongs to tetragonal crystal system, space group is P-42
1M, cell parameter is
α=β=γ=90 °,
Z=2.
2. the preparation method of the Yin with ion-exchange performance of a claim 1-Xi selenides poromerics, it is characterized in that: join N after AgCl, Sn, Se powder sample are weighed up respectively in proportion at 1.25: 1: 3, in N '-solvent dimethylformamide and hydrazine hydrate mixed solvent, room temperature fully stirs in the 28mL stainless steel cauldron that rear inclosure liner is polytetrafluoroethylene (PTFE), in 160 ℃ of solvent thermal reactions, can obtain the peony bulk crystals after a couple of days.
3. the Yin with ion-exchange performance of a claim 1-Xi selenides poromerics is used for as the ion-exchanger of removing nuclear waste radioactive element caesium.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275525A (en) * | 1999-05-27 | 2000-12-06 | 中国科学技术大学 | Solvent thermal synthesis method for nanometer sulfide |
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Granted publication date: 20131113 Termination date: 20180729 |