阅读说明：本技术 新型多元硒化物及其合成方法和在光催化降解染料中的应用 (Novel multi-element selenide, synthetic method thereof and application thereof in photocatalytic degradation of dye ) 是由 张仁春 曹智 王军杰 张道军 赵一冰 李森瑜 刘凡 于 2020-05-13 设计创作，主要内容包括：本发明公开了一种新型多元硒化物,所述化合物的化学式为HenCs[Cu<Sub>2</Sub>GeSe<Sub>5</Sub>],其中en为乙二胺,其骨架结构由无限延展的一维柱状[Cu<Sub>2</Sub>GeSe<Sub>5</Sub>]<Sup>2-</Sup>阴离子链与分立的Cs<Sup>+</Sup>阳离子和质子化的乙二胺组成。该多元硒化物晶体属单斜晶系,空间群为<I>P</I>2(1)/c,晶胞参数为：<I>a</I>=14.5294(4)?,<I>b</I>=9.1733(3)?,<I>c</I>=10.6909(3)?,<I>a</I>=90.0°,<I>β</I>=93.2345°,<I>γ</I>=90.0°。经试验发现,本发明多元硒化物具有良好的光催化性能,可以有效降解染料罗丹明B等。(The invention discloses a novel multi-element selenide, and the chemical formula of the compound is HenCs [ Cu ] 2 GeSe 5 ]Wherein en is ethylenediamine, and the skeleton structure of the ethylenediamine is a one-dimensional column [ Cu ] with infinite extension 2 GeSe 5 ] 2‑ Anionic chains with discrete Cs + Cationic and protonated ethylenediamine. The polyselenide crystal belongs to monoclinic system and has a space group of P 2, (1)/c, unit cell parameters are: a =14.5294(4)Å, b =9.1733(3)Å， c =10.6909(3)Å， a =90.0°， β =93.2345°， γ =90.0 °. Tests show that the multi-element selenide has good photocatalytic performance and can effectively degrade dye rhodamine B and the like.)

1. A novel multielement selenide is characterized in that the chemical formula is HenCs [ Cu₂GeSe₅]Wherein en is ethylenediamine, the polyselenide crystal belongs to a monoclinic system, and the space group isP2, (1)/c, unit cell parameters are:a= 14.5294(4) Å,b=9.1733(3) Å，c= 10.6909(3) Å，a= 90.0°，β= 93.2345°，γ= 90.0°。

2. the method for synthesizing the novel polyeleno selenide of claim 1, wherein Cu, GeO₂Se and CsI are taken as raw materials, ethylenediamine and a solvent are added, ultrasonic dispersion is uniform, then constant temperature reaction is carried out at 140-180 ℃ for 5-7 days, and a product is obtained after the reaction is finished through washing and drying.

3. The method for synthesizing novel polyeleno selenide according to claim 2, wherein the Cu or GeO is₂The molar ratio of Se to CsI is 1: 0.5-2.0: 2-4: 0.5-2.5.

4. The method for synthesizing the novel polyeleno selenide as claimed in claim 2 or 3, wherein the solvent is formed by mixing solution A and solution B, the solution A is a mixed solution of thiophenol and pyridine, and the solution B is a mixed solution of methanol and water; 0.2-0.4 mL of ethylenediamine, 0.2-0.6 mL of solution A, and 0.1-0.3 mL of solution B were added per 0.1 mmol of Cu.

5. Use of the novel polyepiselenide of claim 1 as a photocatalytic material.

6. Use of the novel polyselenides according to claim 5 as photocatalytic material for the photocatalytic degradation of dyes.

7. The use of the novel polyepiselenide of claim 6 as a photocatalytic material, wherein said dye is rhodamine B.

Technical Field

The invention belongs to the technical field of inorganic materials, and particularly relates to synthesis and photocatalytic application of a novel multi-element selenide material.

Background

The crystalline chalcogenide has important application prospects in the fields of photocatalysis, electrocatalysis, fast ion conductance, solar cells and the like due to excellent semiconductor properties of the crystalline chalcogenide. To date, a large number of structurally novel multiple chalcogenides have been investigated and reported and exhibit multifunctional properties, which greatly enrich chalcogenide structural chemistry and material chemistry. [ H.Yang, M.Luo, L.Luo, H.Wang, D.Hu, J.Lin, X.Wang, Y.Wang, S.Wang, X.Bu,Chem. Mater.2016, 28, 8774-8780; D. Sarma, C.D. Malliakas, K.S. Subrahmanyam, S.M.Islam, M.G. Kanatzidis,Chem. Sci.2016, 7, 1121-1132; W. Le, W. Tao, Z. Fan,Z. Xiang, X. Bu, J. Wu, P. Feng,J. Am. Chem. Soc.2010, 132, 3283-3285.]most of the chalcogenides reported at present are composed of main group metals, and although visible light can be partially absorbed, the semiconductor band gap is wide, the absorption of light is weak, and the photocatalytic efficiency is obviously low. [ Y, Zhang, D, Hu, H, Yang, J, Lin, T, Wu,J. Solid State Chem.2017, 251, 61-64; O. Fuhr, S. Dehnen, D. Fenske,Chem. Soc. Rev.2013, 42, 1871-1906; L. Wang, T. Wu, X. Bu, X. Zhao, F. Zuoand P. Feng, Inorg. Chem. 2013, 52, 2259; C. Zhang, M. Ji, S.H. Ji, Y.L. An,Inorg. Chem.2014, 53, 4856-4860.]. In the chalcogenide family, Cu has a rich structural chemistry, the monovalent metal Cu⁺The ions may form multiple chalcogen anion coordination modes, such as linear, planar triangular or tetrahedral geometric coordination. Furthermore, copper-containing chalcogenides have important optoelectronic properties, for example, copper indium gallium selenide is an important photocatalyst and solar conversion material. [ Q, Lin, X, Bu, C, Mao, X, ZHao, K, Sasan and P, Feng,J. Am. Chem.Soc.2015, 137, 6184; J. Lin, Y. Dong, Q. Zhang, D. Hu, N. Li, L. Wang,Y. Liu, T. Wu,Angew. Chem. Int. Ed.2015, 54, 5103-5107; H. Tada, Q. Jin, H.Nishijima, H. Yamamoto. M. Fujishima, S. Okuoka, T. Hattori, Y. Sumida, H.Kobayashi.Angew. Chem. Int. Ed.2011, 50, 3501-3505; J. Xuan, J. Xiao..Angew. Chem. Int. Ed.2012, 51, 6828-6838.]systematic studies have found that the percentage of sunlight utilization by narrow bandgap semiconductors is significantly increased. The Cu can reduce the spectral band gap, the spectral line range of light absorption can be selected in a visible light region, and meanwhile the photoelectric solar energy conversion activity is improved. [ M. -L. Feng, D. Sara, X. -H. Qi, K. -Z. Du, X. -Y. Huang, M.G. Kanatzidis,J. Am. Chem. Soc., 2016,138, 12578–12585; X.-H. Qi, K.-Z. Du, M.-L. Feng, Y.-J. Gao, X.-Y. Huang, M. G.Kanatzidis,J. Am. Chem. Soc., 2017,139, 4314–4317.]. Research on the synthesis and properties of copper-containing multi-element chalcogenides will provide new approaches for further development of novel photovoltaic materials, such as: semiconductors, photocatalysts, electrocatalysts, solar conversion materials, and the like.

Disclosure of Invention

The invention aims to provide a novel multi-element selenide material which is stable in structure, has good photocatalytic performance and can effectively purify and degrade pollutants.

The invention also provides a synthesis method of the novel multi-element selenide and application of the novel multi-element selenide in photocatalytic degradation of dyes.

In order to achieve the purpose, the invention adopts the following technical scheme:

a novel multi-element selenide with the molecular formula of HenCs [ Cu ]₂GeSe₅]Wherein en is ethylenediamine, and the skeleton structure of the ethylenediamine is a one-dimensional column [ Cu ] with infinite extension₂GeSe₅]^2-Anionic chains with discrete Cs⁺Cation and protonated ethylenediamine, and is one expanded one-dimensional multielement structure. Further, the crystal of the novel multi-element selenide belongs to a monoclinic system, and the space group isP2, (1)/c, unit cell parameters are:a= 14.5294(4) Å,b= 9.1733(3) Å,c= 10.6909(3) Å,a=90.0°,β= 93.2345°,γ= 90.0°

the synthesis method of the novel multi-element selenide specifically comprises the following steps: weighing appropriate amount of raw materials Cu and GeO₂Adding a certain amount of ethylenediamine (en) and a solvent into the Se and the CsI, uniformly dispersing by ultrasonic, placing the mixture in a drying box at the temperature of 140-180 ℃ for reaction for 5-7 days, and washing and drying the product after the reaction is finished.

Specifically, the Cu and the GeO₂The molar ratio of Se to CsI is 1: 0.5-2.0: 2-4: 0.5-2.5.

Further preferably, the solvent is formed by mixing a solution A and a solution B, wherein the solution A is a mixed solution of thiophenol (PhSH) and pyridine, and the solution B is a mixed solution of methanol and water; 0.2-0.4 mL of ethylenediamine, 0.2-0.6 mL of solution A, and 0.1-0.3 mL of solution B were added per 0.1 mmol of Cu.

The novel multi-element selenide has photocatalytic performance and can be used as a photocatalytic material; for example, the photocatalyst can be used for degrading dyes, purifying pollutants, degrading organic matters and the like. Furthermore, the novel multi-element selenide has better degradation capability on dye rhodamine B, and the multi-element structure has stable effect in photocatalysis.

Compared with the prior art, the invention has the following beneficial effects:

the invention adopts a mild solvothermal method for synthesis, which is different from a common high-temperature solid-phase method in literature reports and overcomes the defects of high temperature, high risk, low yield, poor repeatability and the like. The synthetic method has the advantages of simple process, mild conditions, high yield and good repeatability, and the multi-element selenide has good photocatalytic performance under the ultraviolet light condition, can be applied to degradation of organic dyes and the like, and injects new vitality for the development of the field of material science.

Drawings

FIG. 1 is a unit structure view of the novel polyselenide of the present invention;

FIG. 2 is a spatial stacking diagram of the novel polyelement selenide of the invention;

FIG. 3 is an XRD pattern of the novel polyelement selenide of the present invention;

FIG. 4 is a UV-VIS spectrum of the novel polyselenides of the present invention;

FIG. 5 is a graph of the absorption of the novel polyelement selenide of the invention by photocatalysis;

fig. 6 is a time chart of the photocatalytic concentration of the novel poly selenide of the present invention.

Detailed Description

In order to make the technical purpose, technical scheme and beneficial effects of the present invention clearer, the technical scheme of the present invention is further described with reference to the accompanying drawings and specific examples, but the examples are intended to explain the present invention and should not be construed as limiting the present invention, the examples do not indicate specific techniques or conditions, the examples are performed according to techniques or conditions described in documents in the field or according to product specifications, and the reagents or instruments are not indicated by manufacturers, and all are conventional products which can be obtained commercially.