过渡金属氮化物活化小分子碳氢化合物的研究
详细信息 查看官网全文
- 英文论文题名：Study on the Activation of Hydrocarbons by Transition Metal Nitrides
- 论文作者：马嘉璧 ; 许琳琳 ; 何圣贵
- 英文论文作者：Jia Bi Ma ; Lin Lin Xu ; Sheng Gui He ; Beijing Institute of Technology ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：北京理工大学;中国科学院化学研究所北京分子科学国家实验室;
- 论文关键词：过渡金属氮化物 ; 量化计算 ; 质谱 ; C-H活化
- 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-第四十四分会：化学动力学
- 语种：中文
- 分类号：O641.3
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十四分会 ; 化学动力学
- 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：303k
- 原文格式：D
- 会议级别：全国
摘要
过渡金属氮化物因具有与Pt等贵金属类似的反应活性而备受关注~([1])。目前,研究人员对金属-氮成键特点、相关的反应机理仍不清楚。近年的气相研究表明可以利用原子团簇作为模型,从分子、电子结构水平对催化剂活性位的构效关系进行研究。我们前期在过渡金属氧化物团簇结构及反应活性方面积累的经验~([2,3])为过渡金属氮化物的研究提供了良好的基础。我们利用质谱结合理论计算研究了两类过渡金属氮化物活化烷烃和烯烃的反应,具体如下:三原子阴离子HNbN~-可以活化甲烷的C-H键并表现出类贵金属Pt的性质(图1)。HNbN~-的活性分子轨道是4d/5s杂化轨道,与Pt原子的活性轨道5d_(z^2)相近,故而展示出与Pt相似的反应活性~([4])。该研究表明合成与贵金属具有相似的活性轨道是利用廉价氮化物代替贵金属的一种可能途径。此外,我们在对Ta_3N_2~-团簇和C_2H_4的反应研究中发现:Ta_3N_2~-可连续与2个C_2H_4反应,活化6个C-H键,释放3个H_2分子。反应过程中可以生成稳定的中间产物Ta_3N_2C_2~-。(图2)
The reactions of some transition metal nitride(TMN) molecules with hydrocarbons by mass spectrometry in-conjunction with density functional theory calculations were investigated. In the reaction of HNb N with CH_4,HNbN~- is capable of activating CH_4 through oxidative addition, exhibiting quite similar reactivities to free Pt atom.The similar electronic structures of HNbN and Pt, especially the similar highest occupied molecular orbitals, are-responsible for this resemblance. In addition, we found that Ta_3N_2~- cluster can activate six C-H bonds in two C_2H_4 molecules, with the release of three H_2. These interesting results inspire us to do more research to investigate the intriguing properties of TMN ions.
The reactions of some transition metal nitride(TMN) molecules with hydrocarbons by mass spectrometry in-conjunction with density functional theory calculations were investigated. In the reaction of HNb N with CH_4,HNbN~- is capable of activating CH_4 through oxidative addition, exhibiting quite similar reactivities to free Pt atom.The similar electronic structures of HNbN and Pt, especially the similar highest occupied molecular orbitals, are-responsible for this resemblance. In addition, we found that Ta_3N_2~- cluster can activate six C-H bonds in two C_2H_4 molecules, with the release of three H_2. These interesting results inspire us to do more research to investigate the intriguing properties of TMN ions.
引文
[1]A.M.Alexander;J.S.J.Hargreaves,Chem.Soc.Rev.2010,39:4388.
[2]J.-B.Ma,B.Xu,J.-H.Meng,X.-N.Wu,X.-L.Ding,S.-G.He,J.Am.Chem.Soc.2013,135:2991.
[3]J.-B.Ma,Z.-C.Wang,Schlangen.M,S.-G.He,Schwarz.H,Angew.Chem.Int.Ed.2013,52:1226.
[4]J.-B.Ma,L.-L.Xu,Q.-Y.Liu,S.-G.He,Angew.Chem.Int.Ed.2016,55:4947.
[2]J.-B.Ma,B.Xu,J.-H.Meng,X.-N.Wu,X.-L.Ding,S.-G.He,J.Am.Chem.Soc.2013,135:2991.
[3]J.-B.Ma,Z.-C.Wang,Schlangen.M,S.-G.He,Schwarz.H,Angew.Chem.Int.Ed.2013,52:1226.
[4]J.-B.Ma,L.-L.Xu,Q.-Y.Liu,S.-G.He,Angew.Chem.Int.Ed.2016,55:4947.