CN104399538A - Compound, preparation method and application thereof as ion exchange material - Google Patents
Compound, preparation method and application thereof as ion exchange material Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
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Abstract
The application of the invention provides a compound, a preparation method and application thereof as an ion exchange material. The compound has a molecular formula shown as below: R1xR22-xSn3S7-y[H2O], wherein R1 and R2 are independently selected from at least one organic ammonium ions, and; x equals to 0 and y is no less than 0. The compound has planar electronegativity [Sn3S7] n2n-skeleton, shows high ion exchange capacity and high selectivity on Cs<+> and Sr<2+> when used as the ion exchange material, and has important significance for treatment of high radioactive element pollution in water environment.
Description
Technical field
The application relates to and a kind ofly has crystalline compounds of layered framework structure and preparation method thereof.
The application also relates to this compound as ion exchange material, is being separated and is removing the application in liquid phase in caesium, strontium.
Background technology
Energy and environment are the two principal themes of current social development always, along with the day by day exhausted of global fossil energy and its environmental problem brought, make the exploitation of nuclear energy more and more receive the concern of people.According to the estimation of Chinese nuclear energy employer's organization, within 2014, China is building nuclear power generating sets 28, and total installation of generating capacity reaches 3,062 ten thousand kilowatts, and the year two thousand twenty predetermined nuclear power installation target will reach 5,800 ten thousand kilowatts.But along with the utilization of nuclear energy, it may bring again the pollution of radioactive element to environment.Such as, after Fukushima, Japan nuclear leakage, near its nuclear power station plant area in seawater, just detect radioactive caesium and strontium element exceeds standard.Because the half-life of these elements is very long, its pollution has become locality and even global environmental problem.Therefore the scavenging material developing radiocesium and strontium element in efficient, cheap removal water environment is extremely important.
Summary of the invention
According to an aspect of the application, provide a kind of compound, this skeletal structure of compound is made up of tin Sn and sulphur S, and component is simply homogeneous, have stronger resistance to acids and bases, and to Cs
+and Sr
2+ion has strong affinity and high selectivity.
Described compound, is characterized in that, has molecular formula as follows:
R
1 xR
2 2-xSn
3S
7·y[H
2O]
Wherein, R
1, R
2independently selected from least one in organoammonium ions; X=0 ~ 2, y>=0.
Described compound is crystal, has tin and sulphur forms electronegative two-dimensional layer skeleton structure, and organic amine cation is positioned at the interlayer of two-dimensional layer skeleton.Electronegative two-dimensional layer skeleton structure that tin and sulphur are formed, can be abbreviated as [Sn
3s
7]
n 2n-layer structure, n be greater than 1 positive integer.
Preferably, described R
1, R
2independently optional be not more than from carbon number 6 organoammonium ions.
Preferably, described R
1, R
2optional at least one in Dimethyl Ammonium ion, trimethyl ammonium ion, ethyl ammonium cations independently.
Described R
1and R
2can be identical organoammonium ions, also can be different organoammonium ions.
Work as R
1and R
2time identical, the molecular formula of described compound can be written as R
1 2sn
3s
7y [H
2o].
Preferably, 20 >=y >=0; Further preferably, 10 >=y >=0; Further preferably, 5 >=y >=0.
Typically, the molecular formula of described compound is:
[Me
2nH
2]
4/3[Me
3nH]
2/3sn
3s
71.25H
2o, this compound molecular weight is 704.5, and belong to monoclinic system, space group is C2/c, and cell parameter is a=22.5651 (10), b=13.0672 (6),
β=101.227 (6) °,
z=8.Sn in this layer structure
4+for pentacoordinate, with S
2-form the trigonal biyramid coordination structure of distortion, the secondary building unit of formation is [Sn
3s
7]; [Sn
3s
7] respectively with around three [Sn
3s
7] by being total to limit ((μ – S)
2) interlink, form the two-dimensional expansion structure containing hexagonal honeycomb shape 24 atom ring being parallel to ab plane.
Wherein, [Me
2nH
2]
+represent dimethylammonium ion, structural formula is:
[Me
3nH]
+represent trimethylammonium ion, structural formula is:
Above compound is only the Typical Representative of compound described in the application, and described in the application, compound is not limited to this.
According to the another aspect of the application, provide a kind of method preparing described compound, the method cost is low, simple process, atom utilization be high, reactant used almost can realize 100% conversion, eliminates the separation difficulty that accessory substance brings.
Described preparation method, is characterized in that, at least containing following steps:
A) Jiang Xiyuan, sulphur source, organic amine and water mixing, obtains the mixture with following proportioning:
The molal quantity of element sulphur and the mole ratio of tin element are S:Sn=1 ~ 4;
The quality of organic amine and the mole ratio of tin element are organic amine: Sn=0.5g/mol ~ 5g/mol;
The quality of water and the mole ratio of tin element are H
2o:Sn=0g/mol ~ 5g/mol;
B) by the mixture of step a) gained in 130 ~ 200 DEG C of crystallization, the solid product obtained through being separated, washing, dry, obtain described compound.
Preferably, step a) in gained mixture the molal quantity of element sulphur and the mole ratio range limit of tin element optionally from 4,3.5,3; Lower limit is optionally from 1,2.5.Further preferably, step a) in gained mixture the molal quantity of element sulphur and the mole ratio of tin element be S:Sn=3.
Preferably, step a) in gained mixture the quality of organic amine and the mole ratio range limit of tin element optionally from 4.0g/mol, 3.5g/mol, 3.0g/mol, 2.0g/mol, 1.8g/mol; Lower limit is optionally from 0.5g/mol, 0.78g/mol, 0.84g/mol, 1.4g/mol, 1g/mol.Preferably, step a) in gained mixture the quality of organic amine and the mole ratio of tin element be organic amine: Sn=0.5g/mol ~ 3.5g/mol.Further preferably, step a) in gained mixture the quality of organic amine and the mole ratio of tin element be organic amine: Sn=0.78g/mol ~ 2g/mol.
Preferably, step a) in gained mixture the quality of water and the mole ratio range limit of tin element optionally from 3.5g/mol, 3.2g/mol, 2.3g/mol, 2.2g/mol, 2g/mol, 1.98g/mol; Lower limit is optionally from 1g/mol, 1.1g/mol, 1.2g/mol, 1.84g/mol, 1.85g/mol.Preferably, the step a) quality of water and the mole ratio H of tin element in gained mixture
2o:Sn=1.1g/mol ~ 3.2g/mol.
Further preferably, step a) in described mixture the mol ratio of element sulphur, tin element and organic amine be S:Sn: organic amine=6:2:3.
Preferably, step a) described in Xi Yuan be selected from containing tetravalent tin ion compound in one or more.Further preferably, step a) in Xi Yuan be stannic chloride pentahydrate.Described butter of tin can not contain the crystallization water.
Preferably, step a) described in sulphur source be selected from sulfur-containing compound, elemental sulfur one or more.Further preferably, step a) described in sulphur source be elemental sulfur.
Preferably, step a) described in organic amine be selected from one or more that carbon number is no more than in the organic amine of 6.Further preferably, step a) described in organic amine be selected from dimethylamine, ethamine, trimethylamine one or more.Further preferably, step a) described in organic amine be dimethylamine.
Preferably, step b) in crystallization temperature be 150 ~ 190 DEG C.
Preferably, step b) described in crystallization, crystallization time is 12 hours ~ 240 hours.Further preferably, crystallization time is 4 days ~ 9 days.
According to the another aspect of the application, provide a kind of ion-exchanger, it is characterized in that, containing above-mentioned arbitrary compound and/or the compound for preparing according to above-mentioned either method.
Described compound is in aqueous to Cs
+, Sr
2+there is good ion-exchange performance.PH can keep higher switching performance and exchange velocity between 0.7 ~ 11, can reach exchange equilibrium state very soon.The water environment of simulated groundwater and nuclear waste, this material is to Cs
+, Sr
2+there is good selective and high distribution coefficient (Kd).
According to the another aspect of the application, provide a kind of ion exchange column, it is characterized in that, containing described ion-exchanger, for separating of or the cesium ion removed in liquid phase and/or strontium ion.Ion exchange column containing described compound, Cs
+clearance can reach more than 96%, and Sr
2+clearance close to 100%.
The beneficial effect of technical scheme described in the application is:
(1) first by [Sn
3s
7]
n 2n-layer structure is applied to removes Cs
+and Sr
2+, compared with the ion exchange material of other kinds such as molecular sieve, clay, to Cs
+and Sr
2+ion has the advantage such as strong affinity and strong acid-fast alkali-proof; The advantages such as contrast with same type of metal chalcogen ion exchange material, it is simply homogeneous that it has material skeleton structure component concurrently, and ion-exchange performance is excellent.
(2) through the Cs of system
+and Sr
2+the experiments such as ion exchange experiments comprises dynamics, Adsorption Model, simulated groundwater and nuclear waste environment, resistance to acids and bases, application ion exchange column confirm the [Sn of Small molecular organic amine guiding
3s
7]
n 2n-the ion exchange material of skeleton is that one removes Cs efficiently
+and Sr
2+novel ion-exchange material.
(3) having general formula is: R
1 xr
2 2-xsn
3s
7y [H
2o] [Sn
3s
7]
n 2n-the ion exchange material of skeleton one-step synthesis can obtain a large amount of pure phase, and atom utilization is high, and synthesis material is relatively inexpensive.
Accompanying drawing explanation
Fig. 1 is the crystal structure schematic diagram of sample 1#, and (a) is [Sn
3s
7]
n 2n-layer structure figure; B () is for being [Sn
3s
7]
n 2n-stratiform accumulation graph.
The crystal structure schematic diagram that Fig. 2 (a) is sample 1#-Cs; B () is Cs
+with Dimethyl Ammonium ion and trimethyl ammonium ion exchange process schematic diagram.
Fig. 3 is the X-ray powder diffraction comparison diagram of sample 1#, sample 1#-Cs, sample 1#-Sr.
Fig. 4 is that sample 1# is to Cs
+, Sr
2+the dynamics figure of ion-exchange.
Fig. 5 is that sample 1# is to Cs
+, Sr
2+the Lang Gemiaoer Adsorption Model fitted figure of ion-exchange, (a) is for sample 1# is to Cs
+the Adsorption Model experiment of ion; B () is for sample 1# is to Sr
2+the Adsorption Model experiment of ion.
Fig. 6 is for sample 1# in simulation nuclear waste hypersaline environment is to Cs
+, Sr
2+distribution coefficient (Kd) figure of ion-exchange.
Fig. 7 be under condition of different pH sample 1# to Cs
+, Sr
2+distribution coefficient (Kd) figure of ion-exchange.
Fig. 8 be in simulate formation water environment sample 1# to Cs
+, Sr
2+distribution coefficient (Kd) figure of ion-exchange.
Fig. 9 is that application of samples 1# simulates ion exchange column to Cs
+, Sr
2+clearance figure.
Detailed description of the invention
Below in conjunction with embodiment, set forth the application further.Should be understood that these embodiments are only not used in the scope of restriction the application for illustration of the application.
If no special instructions, as follows to the test condition of sample in embodiment:
The single crystal X-ray diffraction data of sample are carried out on SuperNova CCD type X-ray diffractometer, Mo target, K α radiation source
Sample and Cs
+the single crystal X-ray diffraction data exchanging the structure of afterproduct are carried out on OxfordXcalibur Eos CCD type X-ray diffractometer, Mo target, K α radiation source
X-ray powder diffraction material phase analysis (XRD) carrying out on the Miniflex II type X-ray diffractometer of Rigaku company at 30kV, 15mA, Cu target, K α radiation source
Atomic absorption spectrum carries out on ContrAA 700 type atomic absorption spectrum spectrometer.
Plasma emission spectroscopy carries out on Ultima 2 type plasma emission spectrometer.
The preparation of embodiment 1 sample 1# ~ sample 6#
Xi Yuan, sulphur source, organic amine and water is even by certain mixed in molar ratio, it is in the stainless steel cauldron of polytetrafluoroethylene (PTFE) that room temperature fully stirs rear inclosure liner, in uniform temperature isothermal reaction a period of time, then Temperature fall is to room temperature, filter and fully wash with distilled water, ethanol, after drying, described compound can be obtained.The relation of the kind of raw material and proportioning, reaction temperature and time, productive rate and sample number into spectrum refers to table 1.
Table 1
Productive rate=(quality of products obtained therefrom) ÷ molal quantity ÷ 3 × product theory molecular weight of tin element (in the tin source) × 100%.
The structural characterization of embodiment 2 sample
X-ray single crystal diffraction is adopted to characterize sample 1# ~ sample 5#, and resolved sample structure by Shelx97.Result show, sample 1# ~ sample 5# all has general formula shown in described compound, below with sample 1# for Typical Representative describes in detail.
The crystal structure of the sample 1# obtained by x-ray single crystal diffraction, this compound molecule formula is [Me
2nH
2]
4/3[Me
3nH]
2/3sn
3s
71.25H
2o, molecular weight is 704.5, and belong to monoclinic system, space group is C2/c, and cell parameter is a=22.5651 (10), b=13.0672 (6),
β=101.227 (6) °,
z=8.
The crystal structure schematic diagram of sample 1# as shown in Figure 1.Fig. 1 (a) is [Sn
3s
7]
n 2n-layer structure figure, wherein white ball represents Sn atom, and the black ball be attached thereto represents S atom.Sn in this layer structure
4+be all pentacoordinate, with S
2-form the trigonal biyramid coordination structure of distortion, the secondary building unit of formation is [Sn
3s
7]; [Sn
3s
7] respectively with around three [Sn
3s
7] by being total to limit ((μ – S)
2) interlink, form the two-dimensional expansion structure containing hexagonal honeycomb shape 24 atom ring being parallel to ab plane.Fig. 1 (b) is [Sn
3s
7]
n 2n-stratiform accumulation graph, Small molecular organic amine is filled in interlayer, white ball larger in figure represents Sn atom, the larger black ball be attached thereto represents S atom, the white ball that interlayer is less represents atom N, the black ball be attached thereto represents C atom, and for clarity, in figure, H atom is omitted.
Embodiment 3 sample 1# ion-exchange performance is tested
Get the solution that 18mL contains 3000ppm cesium chloride, then 18mg sample 1# crystal prototype is added, mixture stirs 20 minutes at 65 DEG C, utilizes atomic absorption spectrum or plasma emlssion spectrometry to determine its Cs the solution of mixture centrifuging and taking supernatant and initial concentration afterwards
+concentration before and after exchanging.Ion-exchange product filters and fully washs successively with distilled water, ethanol and acetone, obtains Cs
+the product of ion-exchange, is designated as sample 1#-Cs.
Get the solution that 18mL contains 100ppm strontium chloride, then 18mg sample 1# crystal prototype is added, mixture stirs 20 minutes at 65 DEG C, utilizes atomic absorption spectrum or plasma emlssion spectrometry to determine its Sr the solution of mixture centrifuging and taking supernatant and initial concentration afterwards
2+concentration before and after exchanging.Ion-exchange product filters and fully washs successively with distilled water, ethanol and acetone, obtains Sr
2+the product of ion-exchange, is designated as sample 1#-Sr.
Sample 1# and Cs
+the sample 1#-Cs obtained after exchange, crystal structure is obtained in test by X ray diffracting data.The crystal structure schematic diagram that Fig. 2 (a) is sample 1#-Cs, wherein white ball represents Sn atom, and the black ball be attached thereto represents S atom, and the larger black ball that interlayer is filled represents Cs atom.Pass through Cs
+mono-crystalline structures after ion-exchange confirms that dimethyl amine cation in sample 1# structure and Trimethylamine cation can completely by Cs
+exchange, see Fig. 2 (b) Cs
+with dimethyl amine cation and Trimethylamine base exchange process schematic diagram.
Fig. 3 is the X-ray powder diffraction comparison diagram of sample 1#, sample 1#-Cs, sample 1#-Sr.Wherein be followed successively by the X-ray diffraction peak of sample 1#-Sr, sample 1#-Cs and sample 1# from top to bottom.Represent Cs
+, Sr
2+after ion-exchange, diffraction maximum moves to high angle direction, after ion-exchange is described, and material layer pitch smaller.
Fig. 4 is that relevant dynamics of ion exchange experiment shows, sample 1# is to Cs
+, Sr
2+the exchange of ion just can reach balance in 5 minutes under 65 DEG C of conditions, wherein Cs under the condition of V (liquor capacity): m (exchanger quality)=278mL/g
+35.38ppm can be dropped to, Sr under the condition of V (liquor capacity): m (exchanger quality)=1000mL/g from 128ppm
2+6.92ppm can be dropped to from 44.31ppm.
Fig. 5 (a) is for sample 1# is to Cs
+the Adsorption Model experiment of ion, shows that it is to Cs
+ion-exchange meet Lang Gemiaoer (Langmuir) model, its degree of fitting R
2=0.9595, to Cs
+the maximal absorptive capacity of ion is 408.9mg/g, is the K of bibliographical information
2xmn
xsn
3-xs
6(x=0.5-0.95) 1.8 times (226mg/g) of (KMS-1).Fig. 5 (b) is for sample 1# is to Sr
2+the Adsorption Model experiment of ion, shows that it is to Sr
2+ion-exchange meet Langmuir model, its degree of fitting R
2=0.9293, to Sr
2+the maximal absorptive capacity of ion is 65.19mg/g.
Fig. 6 is with 5mol/L Na
+the solution coexisted is to simulate nuclear waste, and experiment shows that the Kd value of sample 1# under the hypersaline environment of nuclear waste can reach (Cs respectively
+) 54.15mL/g, (Sr
2+) 22.27mL/g, the metal chalcogenides K more best than the performance of current bibliographical information
2xmg
xsn
3-xs
6(x=0.5-1) (KMS-2) wants high.
Fig. 7 is for being in 0.7 ~ 11 scope at pH, and sample 1# is to Cs
+the Kd value of ion, between 898 ~ 2355mL/g, illustrates that the acid-base value scope that it can be resistance to is large.
Fig. 8 uses certain density Ca
2+(7 ~ 8ppm), Mg
2+(8 ~ 9.7ppm), Na
+(77 ~ 232.5ppm), K
+the mixed solution of (6 ~ 9.1ppm) carrys out simulated groundwater, and experiment shows that this material is to Cs in groundwater environment
+, Sr
2+ion still has higher selective, and when pH=7, its Kd value can reach (Cs respectively
+) 2.146 × 10
2mL/g, (Sr
2+) 3.53 × 10
3mL/g; When pH=11, its Kd value can reach (Cs respectively
+) 1.48 × 10
2mL/g, (Sr
2+) 6.33 × 10
2mL/g.
As can be seen from the above data, there is two-dimentional electronegativity [Sn
3s
7]
n 2n-the described compound of skeleton, as ion exchange material to Cs
+, Sr
2+there is strong ion-exchange capacity and high selective, significant for the high radioactivity element pollution administered in water environment.
Embodiment 4: simulation ion exchange column application
Be prepare with about 3 grams of sample 1# the ion exchange column that packed height is 10 centimetres (being filled with the closed at both ends glass tube that an external diameter is 12 millimeters in the middle of chromatographic column) in the Flash chromatography post of 13.4 millimeters at an internal diameter.With the Cs of this treatment on ion exchange columns certain volume
+and Sr
2+mixed solution (Cs
+concentration is 12 ~ 14.5ppm, Sr
2+concentration is 8.2ppm), collect the solution at column outlet place, the different filtrate volume in interval, sampling detects ion concentration wherein.
Fig. 9 is in simulation ion-exchange column experiments, fills 3 grams of sample 1#, the Cs of coprocessing 2.42L
+and Sr
2+mixed solution (Cs
+concentration is 12 ~ 14.5ppm, Sr
2+concentration is about 8.2ppm), Cs
+clearance remain in 96.13% ~ 98.82% scope, and Sr
2+clearance maintain close to 100% always.
Although the application with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are under the prerequisite not departing from the application's design; can make some possible variations and amendment, the scope that therefore protection domain of the application should define with the application's claim is as the criterion.
Claims (10)
1. a compound, is characterized in that, has molecular formula as follows:
R
1 xR
2 2-xSn
3S
7·y[H
2O]
Wherein, R
1, R
2independently selected from least one in organoammonium ions; X=0 ~ 2, y>=0.
2. compound according to claim 1, is characterized in that, described compound is crystal, has electronegative two-dimensional layer skeleton structure of tin and sulphur formation.
3. compound according to claim 1, is characterized in that, described R
1, R
2one or more in Dimethyl Ammonium ion, ethylammonium ions, trimethyl ammonium ion optional independently.
4. prepare the method for compound described in claim 1, it is characterized in that, at least containing following steps:
A) Jiang Xiyuan, sulphur source, organic amine and water mixing, obtains the mixture with following proportioning:
The molal quantity of element sulphur and the mole ratio of tin element are S:Sn=1 ~ 4;
The quality of organic amine and the mole ratio of tin element are organic amine: Sn=0.5g/mol ~ 5g/mol;
The quality of water and the mole ratio of tin element are H
2o:Sn=0g/mol ~ 5g/mol;
B) by the mixture of step a) gained in 130 ~ 200 DEG C of crystallization, the solid product obtained through being separated, washing, dry, obtain described compound.
5. method according to claim 4, is characterized in that, step a) described in Xi Yuan be selected from containing tetravalent tin ion compound in one or more; Step a) described in sulphur source be selected from sulfur-containing compound, elemental sulfur one or more; Step a) described in organic amine be selected from one or more that carbon number is no more than in the organic amine of 6.
6. method according to claim 4, is characterized in that, step a) described in Xi Yuan be stannic chloride pentahydrate; Step a) described in sulphur source be elemental sulfur.
7. method according to claim 4, is characterized in that, step a) described in organic amine be selected from dimethylamine, ethamine, trimethylamine one or more.
8. method according to claim 4, is characterized in that, step b) described in crystallization, crystallization temperature is 150 ~ 190 DEG C, and crystallization time is 12 hours ~ 240 hours.
9. an ion-exchanger, is characterized in that, containing the compound that the compound described in any one of claims 1 to 3 and/or the method according to any one of claim 5 ~ 8 prepare.
10. an ion exchange column, is characterized in that, containing ion-exchanger according to claim 9, for separating of or the cesium ion removed in liquid phase and/or strontium ion.
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| CN109616234A (en) * | 2018-11-20 | 2019-04-12 | 中国科学院福建物质结构研究所 | A method of for separating and/or extracting radioactive metal cation |
| CN109865537A (en) * | 2019-01-17 | 2019-06-11 | 中国辐射防护研究院 | A kind of calcium alginate-copper ferrocyanide compound ion exchanger and preparation method thereof |
| CN111135875A (en) * | 2019-12-20 | 2020-05-12 | 中国科学院福建物质结构研究所 | Composite ion exchanger, preparation method and application thereof |
| CN114195184A (en) * | 2021-10-27 | 2022-03-18 | 苏州大学 | Preparation method and application of two-dimensional chalcogenide |
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| CN105080623A (en) * | 2015-08-14 | 2015-11-25 | 中国科学院福建物质结构研究所 | Ion exchanger for separating and/or extracting rare earth elements |
| CN105080623B (en) * | 2015-08-14 | 2018-02-16 | 中国科学院福建物质结构研究所 | A kind of ion-exchanger for being used for separation and/or Extraction of rare earth element |
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| CN109865537A (en) * | 2019-01-17 | 2019-06-11 | 中国辐射防护研究院 | A kind of calcium alginate-copper ferrocyanide compound ion exchanger and preparation method thereof |
| CN111135875A (en) * | 2019-12-20 | 2020-05-12 | 中国科学院福建物质结构研究所 | Composite ion exchanger, preparation method and application thereof |
| CN114195184A (en) * | 2021-10-27 | 2022-03-18 | 苏州大学 | Preparation method and application of two-dimensional chalcogenide |
| CN114195184B (en) * | 2021-10-27 | 2023-02-10 | 苏州大学 | Preparation method and application of two-dimensional chalcogenide |
| WO2023070930A1 (en) * | 2021-10-27 | 2023-05-04 | 苏州大学 | Two-dimensional chalcogen compound, and preparation method therefor and application thereof |
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