二硫化硒的制备及其在洗护领域的应用研究进展

doi:10.3969/j.issn.2097-2806.2024.04.013

摘要/Abstract

摘要：

二硫化硒是硫化硒（Se_mS_n）混合物的统称，具有多元环结构，不同环结构之间可相互转化。二硫化硒常用熔融法、化学法合成，而纳米二硫化硒常用电化学法和绿色合成法制备，其常用的表征方法有X射线衍射分析（XRD）、扫描电镜（SEM）、透射电镜（TEM）、X射线能量光谱仪（EDS）、动态光散射（DLS）和傅里叶红外光谱（FT-IR）。二硫化硒属于细胞生长抑制剂和角质溶解剂，具有抗皮脂溢出、抗真菌及细菌的作用，能抑制核分裂，造成表皮细胞更替减少，起到止痒、消炎、减少脱屑的作用，常用于治疗脂溢性皮炎和花斑藓。硫和硒都是具有多种原子价位的元素，既可表现还原性，又可表现氧化性，其潜能让二硫化硒的分子结构、性能特点及应用开发成为研究热点。本文综述了二硫化硒性质、结构特点、制备方法、表征及其在洗护领域的应用，并对其未来发展趋势进行了展望。

关键词: 二硫化硒, 纳米材料, 制备, 皮炎

Abstract:

Selenium disulfide is a generic term for mixtures of Se_mS_n with a polycyclic ring structure, which has different ring structures interconverting with each other in the molten and solution states. Selenium disulfide is commonly synthesized by fusion and chemical methods, while nanosized selenium disulfide is commonly synthesized by electrochemical and green synthesis methods. Its commonly used characterization methods are X-ray diffraction analysis （XRD）, Scanning electron microscope （SEM）, Transmission electron microscope （TEM）, X-ray energy spectrometry （EDS）, Dynamic light scattering （DLS） and Fourier transform infrared spectrometer （FT-IR）. Selenium disulfide is a cell growth inhibitor and a keratolytic agent, with anti-seborrhea, anti-fungal and anti-bacterial effects, which can inhibits nuclear division, resulting in reduced epidermal cell turnover. It is commonly used in the treatment of seborrheic dermatitis and lichen planus because of its antipruritic, anti-inflammatory and anti-dandruff properties. Sulfur and selenium are both elements with multiple atomic valences that can exhibit both reducing and oxidizing properties. Their potential has made the molecular structure, performance characteristics and application development of selenium disulfide a research hotspot. This paper reviews the selenium disulfide properties, structural features, preparation methods, characterization and applications, and gives an outlook on its future development trend.

Key words: selenium disulfide, nanomaterials, preparation, dermatitis

中图分类号:

TQ658.3

王诗琼, 刘晓纯, 蓝云萍, 孔祥灵, 陈来成, 何秋星. 二硫化硒的制备及其在洗护领域的应用研究进展[J]. 日用化学工业（中英文）, 2024, 54(4): 467-476.

Shiqiong Wang, Xiaochun Liu, Yunping Lan, Xiangling Kong, Laicheng Chen, Qiuxing He. Research progress on the preparation of selenium disulfide and its application in the field of toiletries[J]. China Surfactant Detergent & Cosmetics, 2024, 54(4): 467-476.

图/表 10

No.	Year	Name	Structure	Selenium-sulfur molar ratio	Crystal group	Crystal system	Lattice constant （a/b/c/α/β/γ）
23681	1970	Sulfur Selenium （5/4）	Se4 S5	1.97	P 31	Trigonal/ Rhombohedral	7.850/7.850/4.620/ 90.0/90.0/120.0
52095	1973	Sulfur Selenium （10.5/1.5）	Se1.5 S10.5	0.35	P n n m	Rhombic	4.774/9.193/14.680/ 90.0/90.0/90.0
650859	1977	Sulfur Selenide （4.7/3.3）	Se3.296 S4.704	1.73	P 1 2/c 1	Monoclinic	8.579/13.405/9.354/ 90.0/124.1/90.0
1354	1977	Selenium Sulfur （2.9/5.1）	Se2.9 S5.1	1.40	P 1 2/c 1	Monoclinic	8.578/13.386/9.368/ 90.0/124.3/90.0
1355	1977	Selenium Sulfur （3.34/4.66）	Se3.34 S4.66	1.77	P 1 2/c 1	Monoclinic	8.579/13.405/9.354/ 90.0/124.1/90.0
1356	1977	Selenium Sulfur （4.69/3.21）	Se4.69 S3.21	3.61	P 1 21/n 1	Monoclinic	8.737/9.104/11.316/ 90.0/90.8/90.0
1535	1978	Selenium Sulfur （3.02/4.98）	Se3.02 S4.98	1.50	P 1 2/c 1	Monoclinic	8.564/13.354/9.368/ 90.0/124.3/90.0
9760	1979	Heptasulfur Selenium	Se1 S7	0.35	P 1 2/c 1	Monoclinic	8.498/13.134/9.311/ 90.0/124.9/90.0
9761	1979	Hexasulfur Diselenium	Se2 S6	0.82	P 1 2/c 1	Monoclinic	8.596/13.374/9.392/ 90.0/124.3/90.0
9762	1979	Tetrasulfur Tetraselenium	Se4 S4	2.47	P 1 21/n 1	Monoclinic	8.750/9.139/11.360/ 90.0/91.0/90.0
9763	1979	Trisulfur Pentaselenium	Se5 S3	4.11	P 1 21/n 1	Monoclinic	8.867/9.310/11.456/ 90.0/90.8/90.0
26538	1981	Selenium Sulfur （1.1/6.9）	Se1.1 S6.9	0.39	P 1 2/c 1	Monoclinic	8.340/13.110/9.300/ 90.0/123.9/90.0
26539	1981	Selenium Sulfur （3.7/4.3）	Se3.7 S4.3	2.12	P 1 2/c 1	Monoclinic	8.400/13.260/9.370/ 90.0/124.5/90.0
24824	1982	Cyclo-selenium Sulfur（2.57/5.43）	Se2.57 S5.43	1.17	P 1 2/c 1	Monoclinic	8.550/13.340/9.336/ 90.0/124.2/90.0
61134	1986	Pentaselenium Sulfide	Se5 S1	12.34	R-3 H	Trigonal/ Rhombohedral	11.243/11.243/4.374/ 90.0/90.0/120.0
61135	1986	Selenium Sulfide （5.1/1.9）	Se5.1 S1.9	6.62	P 21 21 21	Rhombic	13.574/12.924/4.352/ 90.0/90.0/90.0
657289	1992	Selenium Sulfide （0.72/0.29）	Se0.72 S0.29	6.13	P 31 2 1	Trigonal/ Rhombohedral	4.370/4.370/ 4.954/ 90.0/90.0/120.0

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Type	Preparation	Reference
Fusion	Se+2S → SeS₂	[10，11]
Chemical	SeO₂+2Na₂S+2H₂O → SeS₂+4NaOH	[12]
	SeO₂+2（NH₄）₂S → SeS₂+4NH₃↑+ 2H₂O	[12]
	SeO₂ and R-CS-NH-CH₂-C₆H₅to form SeS₃	[12]
	H₂SeO₃+2Na₂S+4CH₃COOH → SeS₂↓+4CH₃COONa+3H₂O	[12]
	H₂SeO₃+2（NH₄）₂S+4CH₃COOH → SeS₂↓+4CH₃COONH₄+3H₂O	[13]
	H₂SeO₃+2NH₄HS+2CH₃COOH → SeS₂↓+2CH₃COONH₄+3H₂O	[13]
	Na₂SeO₃+2Na₂S+6HCl → SeS₂↓+6NaCl+3H₂O	[14]
Chemical	Na₂SeO₃+2CH₃CSNH₂+H₂O → SeS₂↓+2CH₃CONH₂+2NaOH	[15]
	H₂Se+S₇Cl₂→ SeS₇↓+2HCl	[16]
	8H₂Se+8S₂Cl₂→ Se₂S₆↓+2Se₃S₅↓+ 16HCl	[17]
	A mixture of SCl₂ and Se₂Cl₂ reacts with KI to form Se_nS₈_-n	[18]
	H₂S_n with Se₂Cl₂ and SeCl₄ to form Se_nS₈_-n and Se_nS₁₂_-n	[19]
	Se₂Br₂ reacts with H₂S to form Se_1.1S_6.9 and Se_3.7S_4.3	[20]
	[Ti（C₅H₅）₂S₅]+Se₂Cl₂→ Se₂S₅+[Ti（C₅H₅）₂Cl₂]	[21]
	2Se₂S₅→ Se₃S₅+SeS₅	[21]
	[Ti（C₅H₅）₂Se₅]+SCl₂→ Se₅S+[Ti（C₅H₅）₂Cl₂]	[22]
	[Ti（C₅H₅）₂Se₅]+S₂Cl₂→ Se₅S₂+[Ti（C₅H₅）₂Cl₂]	[22]
Electrochemical/Photo	Electrolytic reduction of H₂SO₄/H₂SeO₄ mixtures	[12]
Electrochemical/Photo	Se₈ is irradiated in sunlight for 1-2 hours, and reflux can form various selenium sulfide rings	[23]

Type	Preparation	Reference
Chemical	H₂SeO₃+2（NH₄）₂S+AG → AG-SeS₂NPs↓+4NH₃↑+3H₂O	[24]
Electrochemical	SeCl₄ Se⁴⁺+4e^-（Electrodes）	[25]
	Na₂S+2H₂O 2NaOH+S^2-+H₂（Solution）	[25]
	Se⁴⁺+2S^2- SeS₂（Solution）	[25]
	NaHSeO₃+2Na₂S+5CH₃COOH → SeS₂↓+5CH₃COONa+3H₂↑	[27]
Green synthesis	Formation of nano-SeS₂ by microbial reduction of sulfide-selenite mixture in sludge	[28]
	Synthesis of nano-SeS₂ by Saccharomyces cerevisiae	[29]
	2Na₂S+SeCl₄ → SeS₂↓+4NaCl	[30]

Instrument name	Chemical bond information	Reference
FT-IR	S-S: 452 cm^-1, Se-S: 320-340 cm^-1, Se-Se: 260-280 cm^-1	[30]
	S-S: 462-488 cm^-1, Se-S: 270-290 cm^-1, Se-Se: 371-390 cm^-1	[31]
	Se-S: 340-386 cm^-1	[32]
	S-S: 309-455 cm^-1, Se-Se: 244-280 cm^-1	[33]
Raman	Se-S: 320-400 cm^-1, -S-Se-S-: 320-340 cm^-1 and 380-400 cm^-1, -S-Se_n-S-: 360 cm^-1, Se-Se: 260 cm^-1	[12]

Ingredients	Mechanism	Advantages and Disadvantages	Maximum additive volume （China）	Maximum additive volume （EU）
CLM	Inhibit dandruff-causing fungus	Cheap, Stable to light, heat, metal ions, No discoloration; Poor anti-dandruff effect, Tolerance	Preservative: 0.5%	Preservative: 0.5%
OCT	Kill fungus, Act as a defense against oxidation, Break down peroxides	Good compatibility, Non-irritating; Average anti-dandruff effect, Yellowing in the presence of iron and copper ions, Tolerance	Elution type: 1%	Elution type preservatives: 1.0%
ZPT	Inhibit the growth of Gram-positive, Gram-negative bacteria and molds	Cheap; Average anti-dandruff effect, Unstable to light and oxidizers, Risk of carcinogenicity, Mutation, Reproductive toxicity	Anti-dandruff shower: 1.5% Stationary type of hair: 0.1% Elution type preservative: 0.5%	Prohibit
HD100	Inhibit and kill Gram-positive, Gram-negative bacteria, molds and yeasts	Good compatibility, Non-irritating, Good anti-dandruff effect; Expensive	Preservative: 0.1%	Preservative: 0.1%
SA	Inhibit and kill fungus and bacteria, Soften the stratum corneum, Promote exfoliation, Reduce fungal hyphae	Good anti-dandruff effect; Effective only in acidic environments, High irritating	Shampooing for Hair: 3% Shampoo preservatives: 0.5%	Shampoo: 3% Shampoo preservative: 0.5%
SeS₂	Anti-bacterial, Anti-fungal, Anti-viral, Cell growth inhibitor, Keratolytic agent	Obvious anti-dandruff effect; Higher irritation	Anti-dandruff shampoo: 1%	Shampoo: 1%
Ketoconazole	Inhibition of ergosteroid synthesis in fungal cell membranes, Affecting cell membrane permeability	Obvious anti-dandruff effect; Hepatotoxic	Prohibit	Prohibit