Crystalline metal chalcogenides have unique physical and chemical properties, which have potential application value in electrochemistry, ion exchange, photocatalysis, gas adsorption and other fields. They are one of the functional materials widely concerned by people. Therefore, in order to obtain more thioarsenate compounds with novel structure and excellent performance, Professor Xiong Weiwei of Nanjing University of technology and researcher Hu Bing of Fujian Institute of material structure have recently prepared a series of thioarsenate compounds with novel structure by developing a new synthesis strategy and using organic amine / mercaptan mixed solvothermal synthesis method.
Generally, crystalline metal chalcogenides can be synthesized by several traditional methods, including high-temperature solid-state method, molten salt method, water (solvent) heat method, room temperature solution method, and several new strategies, such as ionic heat and surfactant heat method, have emerged in recent years. Among them, water (solvothermal) method is widely used to synthesize new metal chalcogenides because of its mild reaction conditions and easy formation of metastable phase structure. However, the solubility of some binary sulfur compounds v2vi3 (v = as, Sb, Bi; VI = s, Se, TE) and Se in water or traditional organic solvents is very low, which is easy to separate from the reaction by precipitation from the solvent system, thus hindering the further development of sulfur reaction and restricting the synthesis of crystalline metal sulfur compounds. Obviously, the solvent will seriously affect the synthesis of crystalline metal chalcogenides. Therefore, it is very important to explore new solvent systems for the synthesis of new crystalline chalcogenides.
The mixed solvent of mercaptan and amine is cheap and has strong dissolving ability to the binary phase metal chalcogenide. This solvent system has been widely used in the preparation of metal sulfur based semiconductor film devices. However, this mixed solvent system has not been used for the preparation of novel crystalline metal chalcogenides. Therefore, Professor Xiong Weiwei's team used 1:1 volume ratio of n-butylamine (BA) / 1,2-ethyldithiol (EDT) mixed solvent as the reaction medium to dissolve As2S3, s and se. With piperazine cation as the structure guide agent, nine new crystalline thioarsenate compounds were synthesized and their photocurrent properties were tested.
Figure 1. Synthesis of thioarsenate in mercaptan amine mixed solvent.
In the synthesis of these thioarsenates, the researchers found that the type and proportion of mercaptans and amines can directly affect the structure and components of thioarsenates, and the reaction temperature can promote the structural transformation of the compounds. If the reaction temperature is raised, the disulfide S-S bond in the one-dimensional chain [ass (S2)] NN - of compound 5 will break and gradually change into one-dimensional chain [Ass 2] NN - of compound 6. In addition, if n-butylamine or 1,2-ethanedithiol is used as the solvent alone, these thioarsenates can not be synthesized, which shows that the mixed solvent system of n-butylamine and 1,2-ethanedithiol is very important for the formation of these thioarsenates. The solvothermal method of mercaptan amine mixture provides a new way for the preparation of new crystalline metal sulfur compounds.
Figure 2. Photocurrent response of thioarsenate.
This achievement was recently published on organic chemistry. The first authors of this article are Wang Fei and Yang Dandan, master degree students of Nanjing University of technology.
Original text (scan or long press QR code, and then go to the original page after identification): combining crystal chalcogenidoarsenates in thiol – amine solution mixturesfei Wang, Dan Yang, Yi Yu Liao, Zhong Jie Ma, Bing Hu, Yan Qi Wang, Wei Wei Xiong, Xiao Ying huanginorg. Chem., 2020, 59, 4, 2337-2347, DOI: 10.1021/acs.inorgchem.9b03165
About Dr. Xiong Weiwei
Xiong Weiwei, professor and doctoral supervisor of Advanced Materials Research Institute of Nanjing University of technology. In 2012, he obtained a doctor's degree from Fujian Institute of material structure, Chinese Academy of Sciences. From 2012 to 2015, he worked in Nanyang University of technology, Singapore, and since April 2015, he has worked in Nanjing University of technology.
The research area focuses on the development of new synthesis technology for the synthesis of crystalline functional materials with novel structure and excellent performance, and the development of such materials in energy and environmental catalysis. He has published more than 50 papers in international academic journals such as J. am. Chem. SOC., angel Chem int. ed., chem. SCI., appl. Catalyst. B: environ., chem. Commun., ACS appl. Mater. Interfaces, inorg. Chem., inorg. Chem. Front., etc., and cited more than 1900 times by SCI. It has been supported by general program of National Natural Science Foundation of China, special professor of Jiangsu Province, youth program of Natural Science Foundation of Jiangsu Province and "six talent peaks" of Jiangsu Province.
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