摘要
镍硫化物因其独特的电子结构,优异的电学、磁学、催化特性引起了广泛关注.本研究以氯化胆碱-乙二醇(ChCl-EG)、氯化胆碱-尿素(ChCl-Urea)、乙酰胺-乙二醇(C2H5NO-EG)、甜菜碱盐酸盐-乙二醇(Betaine·HCl-EG)等4种低共熔溶剂(DESs)为溶剂,以Ni(CH3COO)_(2)·4H_(2)O、Na_(2)S_(2)O_(3)·5H_(2)O为反应物,在常压、120℃的条件下合成出了α-NiS、β-NiS和Ni3S4等镍硫化物粉末.为优选出合成镍硫化物较为适宜的低共熔溶剂类型,实验考察了DESs种类、反应物配比对合成产物的组成、形貌及质量的影响,研究了DESs的稳定性.结果表明,DESs作为反应介质在合成过程中充当了反应溶剂和形貌控制剂.与C_(2)H_(5)NO-EG和Betaine·HCl-EG相比,在ChCl-EG和ChCl-Urea中合成的产物分散性更好,且ChCl-EG和ChCl-Urea稳定性优于C_(2)H_(5)NO-EG和Betaine·HCl-EG.热重和红外分析表明,ChCl-EG、ChCl-Urea分别在120、176℃内具有较好的热稳定性,其反应后仍保持结构稳定.因此,ChClEG、ChCl-Urea更适宜作为反应溶剂合成镍硫化物.
Nickel sulfides have attracted considerable attention in the fields of supercapacitors,photocatalysis,and water electrolysis due to their excellent catalytic activity,electrical conductivity,and magnetic properties.However,traditional solvothermal synthesis of nickel sulfides typically requires hydrothermal kettles or autoclaves,which involve complex operations and stringent equipment demands.As an alternative,deep eutectic solvents(DESs)-formed by eutectic mixtures of hydrogen bond acceptors and donors,offer notable advantages.Compared to conventional solvents,DESs exhibit superior solubility,low vapor pressure,and good chemical stability,making them increasingly popular in catalysis and materials synthesis.Owing to these properties,DESs can be employed as reaction media under ambient pressure,eliminating the need for highpressure equipment.This study explores the feasibility of using DESs as green solvents for the synthesis of nickel sulfides.Four DESs were investigated:choline chloride-ethylene glycol(ChCl-EG),choline chlorideurea(ChCl-Urea),acetamide-ethylene glycol(C₂H₅NO-EG),and betaine hydrochloride-ethylene glycol(Betaine·HCl-EG).Nickel acetate tetrahydrate(N(i CH_(3)COO)_(2)·4H_(2)O)and sodium thiosulfate pentahydrate(Na_(2)S_(2)O_(3)·5H_(2)O)were used as reactants.The effects of DESs types and reactant ratios on product composition,morphology,and mass were systematically studied,along with the thermal and structural stability of four DESs.The results showed that α-NiS,β-NiS,and Ni₃S₄powders were successfully synthesized in ChCl-EG,ChCl-Urea,and C₂H₅NO-EG at 120℃ for 12 hours under atmospheric pressure.In contrast,the use of Betaine·HCl-EG resulted in a mixture of S,NiS_(2),and NiSO_(4)·6H_(2)O.Morphological analysis revealed that DESs suppressed particle diffusion and grain growth,thereby promoting the formation of nano-scale nickel sulfide particles.Moreover,DESs served dual functions as both solvents and morphology-controlling agents.Products synthesized in ChCl-EG and ChCl-Urea DESs exhibited better dispersibility compared to those from C_(2)H_(5)NO-EG and Betaine·HCl-EG,and these DESs also produced higher yields of nickel sulfide.Stability analyses demonstrated that ChCl-EG and ChCl-Urea DESs possessed superior thermal and structural stability compared to the other DESs.Thermogravimetric analysis confirmed that ChCl-EG and ChCl-Urea DESs were thermally stable up to 120℃ and 176℃,respectively,while Fourier-transform infrared spectroscopy indicated that their molecular structures remained intact post-reaction.In conclusion,ChCl-EG and ChCl-Urea DESs are shown to be effective and stable green solvents for the ambient-pressure synthesis of highquality nickel sulfide powders.
作者
张远
黄平
吴恩辉
覃治杰
侯静
刘鹏
徐众
李军
ZHANG Yuan;HUANG Ping;WU En-Hui;QIN Zhi-Jie;HOU Jing;LIU Peng;XU Zhong;LI Jun(College of Vanadium and Titanium,Panzhihua University,Panzhihua 617000,China;Vanadium and Titanium Critical Strategic Materials Key Laboratory of Sichuan Province,Panzhihua 617000,China)
出处
《四川大学学报(自然科学版)》
北大核心
2025年第4期940-949,共10页
Journal of Sichuan University(Natural Science Edition)
基金
攀枝花市指导性科技项目(2020ZD-S-28)
攀枝花学院校级项目(2023YB05)
四川钒钛产业发展研究中心开放项目(2023VTCY-Y-03)。
关键词
镍硫化物
氯化胆碱-乙二醇
氯化胆碱-尿素
低共熔溶剂
常压
Nickel sulfides
Choline chloride-ethylene glycol
Choline chloride-urea
Deep eutectic solvents
Normal pressure
