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基于软硬酸碱理论的单分散中重稀土硫氧化物纳米板的可控合成
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:TQ325.2[化学工程—合成树脂塑料工业]
  • 作者机构:[1]稀土材料化学及应用国家重点实验室北京大学-香港大学稀土材料和生物无机化学联合实验室北京大学化学与分子工程学院北京分子科学国家实验室,北京100871
  • 相关基金:国家自然科学基金(Nos.21025101,21271011)资助
中文摘要:

根据软硬酸碱理论,中重稀土+3价离子硬度高,与S2离子亲合能力弱,而与O2离子亲合能力强,因此很难通过基于高沸点有机溶剂的前驱体热分解法合成中重稀土硫氧化物纳米材料.发展了制备掺杂或非掺杂的中重稀土(Eu,Gd,Er,Y,Yb)的单分散硫氧化物纳米板的前驱体热分解方法.密度泛函理论计算表明,从轻稀土元素到中重稀土元素,合成硫氧化物所需要的硫元素化学势逐渐升高.实验结果表明:在油胺中以H2S气体为硫化试剂,以分解温度低的稀土乙酰丙酮盐为前驱体在280℃条件下反应,可以有效提高反应体系中硫元素的化学势,从而利于目标硫氧化物纳米晶的生成.其中,所获得的Y2O2S:Eu纳米板在251 nm紫外光激发下可发出红色荧光;而与体相材料相比,因其表面原子比例很高且晶化度较低,导致其荧光寿命较短、量子产率较低.

英文摘要:

Based on the theory of hard and soft acids and bases,trivalent ions of middle and heavy rare earths belong to very hard acids,which possess weak affinity towards S2 ions but strong affinity to O2 ions.So it is difficult to synthesize middle and heavy rare earth oxysulfide nano-materials through the thermolysis method in high-boiling-point organic solvent.In this article,monodispersed oxysulfide nanoplates of Y,Eu,Gd,Er and Yb were synthesized through this thermolysis method we developed.Both sodium-doped and undoped rare earth oxysulfide nanoplates could be prepared,and the doping of sodium ions could promote the crystallization of the nanoplates.Rare earth acetylacetonates were used as metal precursors and H2S gas as the sulfurizing reagent.The reactions were conducted in oleylamine at 280 ℃ for 1 hour.The thermogravimetric analysis of the precursor showed that the initial decomposition temperature of the rare earth acetylacetonates is about 200 ℃,which is much lower than that of rare earth oleates.The transmission electron microscopy observation and energy dispersive X-ray analyses of the intermediate products during the synthesis of the nanoplates showed that rare earth oxide nanoplates formed firstly at about 220 ℃,and these nanoplates transformed to oxysulfide nanoplates gradually during the temperature ramping period.Density functional theory calculation was used to compare the total free energy of the oxide and oxysulfide of different rare earth elements.According to this thermodynamical comparison,we concluded that,from light rare earths to heavy rare earths,higher chemical potential of sulfur is needed to obtain the oxysulfide rather than oxide.On one hand,H2S gas has higher sulphurizing power than sulfur.On the other hand,a comparatively low reaction temperature favors the dissolving of H2S in oleylamine.As a result,the chemical potential of sulfur in synthetic system could be effectively increased by using rare earth acetylacetonates as the precursors instead of rare earth oleates,and using H2S g

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期刊信息
  • 《化学学报》
  • 北大核心期刊(2014版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院上海有机化学研究所
  • 主编:周其林
  • 地址:上海市零陵路345号
  • 邮编:200032
  • 邮箱:hxxb@sioc.ac.cn
  • 电话:021-54925085
  • 国际标准刊号:ISSN:0567-7351
  • 国内统一刊号:ISSN:31-1320/O6
  • 邮发代号:4-209
  • 获奖情况:
  • 首届国家期刊奖,第二届国家期刊奖提名奖,中国期刊方阵“双高期刊”
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:28694