电喷雾质谱研究[Mn_(15)~ⅡMn_4~Ⅲ(L)_(18)(OH)_(12)(N_3)_6](CIO_4)_6的生长机理
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- 英文论文题名：Probing the Formation of [Mn_(15)~Ⅱ15Mn_4~Ⅲ(L)_(18)(OH)_(12)(N_3)_6](ClO_4)_6 by Electrospray Ionization Mass Spectrometry
- 论文作者：苏海峰 ; 邓永恺 ; 孙頔 ; 林水潮 ; 郑兰荪
- 英文论文作者：Hai Feng Su ; Yong Kai Deng ; Di Sun ; Shui Chao Lin ; Lan Sun Zheng ; State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry ; College of Chemistry and Chemical Engineering ; Xiamen University ; Key Lab of Colloid and Interface Chemistry ; Ministry of Education ; School of Chemistry and Chemical Engineering ; Shandong University
- 年：2016
- 作者机构：厦门大学固体表面物理化学国家重点实验室化学化工学院;山东大学化学化工学院;
- 论文关键词：金属团簇 ; 电喷雾质谱 ; 生长机理
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十三分会：质谱分析
- 语种：中文
- 分类号：O657.63;O641.4
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十三分会 ; 质谱分析
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：146k
- 原文格式：D
- 会议级别：全国
摘要
金属纳米团簇的合成在近几年取得的突飞猛进的发展。然而,由于生长过程复杂、缺乏实时监测手段等原因,金属纳米团簇的生长机理一直是该领域研究的重点和难点。质谱由于检测速度快、化学特异性强、灵敏度高,非常适合表征金属纳米团簇的形成过程。本工作将电喷雾质谱应用于表征金属团簇[Mn~Ⅱ_(15)Mn~Ⅲ_4(L)_(18)(OH)_(12)(N_3)6](ClO_4)_6的合成过程,成功检测到四种团簇中间体Mn_7,Mn_(10),Mn_(12)和Mn_(14),跟踪发现其质谱信号随反应时间推移先增强后逐渐衰减,于反应90分钟时显最大值;而产物Mn_(19)的质谱信号持续增强。质谱手段揭示了Mn_(19)簇的形成机理:单核Mn首先组装成Mn_7簇,Mn_7可形成Mn_(10)、Mn_(12)、Mn_(14)中间体,小团簇中间体生长到一定程度逐渐转变成更大的、热力学更稳定的Mn_(19)簇。
Recently,a great progress has been made in synthesizing metal nanoclusters,however,due to complexity of the synthesis process and lack of in-situ characterization technologies,details of their formation mechanism remain challenging.Because of its advantage of speed,chemical specificity,low detection limits,electrospray ionization mass spectrometry(ESI-MS) was applied in this work and four intermediate clusters(Mn_7,Mn_(10),Mn_(12),and Mn_(14))were successfully identified in the synthesis process of[Mn_(15)~Ⅱ Mn_4~Ⅲ(L)_(18)(OH)_(12)(N_3)_6](C1O_4)_6.In the time-dependent ESI-MS study,the peak intensities of Mn_7,Mn_(10),Mn_(12),and Mn_(14) species were gradually decreased after 90 min,whereas intensity of Mn_(19) species increased further to a maximum at 330 min,which indicated these smaller intermediates gradually transformed to the larger and thermodynamically stable Mn_(19) disc.Accordingly,the detail of a hierarchical step-by-step formation from monomer(Mn) to heptamer(Mn_7) to nonadecamer(Mn_(19)) was elucidated.
Recently,a great progress has been made in synthesizing metal nanoclusters,however,due to complexity of the synthesis process and lack of in-situ characterization technologies,details of their formation mechanism remain challenging.Because of its advantage of speed,chemical specificity,low detection limits,electrospray ionization mass spectrometry(ESI-MS) was applied in this work and four intermediate clusters(Mn_7,Mn_(10),Mn_(12),and Mn_(14))were successfully identified in the synthesis process of[Mn_(15)~Ⅱ Mn_4~Ⅲ(L)_(18)(OH)_(12)(N_3)_6](C1O_4)_6.In the time-dependent ESI-MS study,the peak intensities of Mn_7,Mn_(10),Mn_(12),and Mn_(14) species were gradually decreased after 90 min,whereas intensity of Mn_(19) species increased further to a maximum at 330 min,which indicated these smaller intermediates gradually transformed to the larger and thermodynamically stable Mn_(19) disc.Accordingly,the detail of a hierarchical step-by-step formation from monomer(Mn) to heptamer(Mn_7) to nonadecamer(Mn_(19)) was elucidated.
引文
[1]Deng,Y.-K.;Su,H.-F.;Lin,S.-C.;Sun,D;Zheng,L.-S.et al J.Am.Chem.Soc.2016,138:1328.