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题名: Charge transfer between triphenyl phosphine and colloidal silver: A SERS study combined with DFT calculations
作者: Hu, Gengshen;  Feng, Zhaochi;  Han, Difei;  Li, Jun;  Jia, Guoqing;  Shi, Jianying;  Li, Can
通讯作者: 李灿
刊名: JOURNAL OF PHYSICAL CHEMISTRY C
发表日期: 2007-06-21
DOI: 10.1021/jp0703915
卷: 111, 期:24, 页:8632-8637
收录类别: SCI
文章类型: Article
部门归属: 5
项目归属: 503
产权排名: 1;1
WOS标题词: Science & Technology ;  Physical Sciences ;  Technology
类目[WOS]: Chemistry, Physical ;  Nanoscience & Nanotechnology ;  Materials Science, Multidisciplinary
研究领域[WOS]: Chemistry ;  Science & Technology - Other Topics ;  Materials Science
英文摘要: The adsorption of triphenyl phosphine (PPh3) on colloidal silver has been investigated by means of surface-enhanced Raman spectroscopy (SERS). On the basis of surface selection rule, it is deduced from SERS results that PPh3 adsorbs on silver surface via its P atom with three phenyl rings tilted with respect to the silver surface. The electron-donor effect of PPh3 can be sensitively probed by the coadsorbed SCN-. The Raman frequency of nu(CN) of the adsorbed SCN- shifts to lower frequencies when PPh3 is coadsorbed with SCN-, and the red shift of CN stretching frequency is found to increase with increasing the surface coverage of PPh3. This could be explained in terms of the electron-donor effect of PPh3: PPh3 adsorbed on silver surface donates its lone pair of electrons to silver surface, and then the negative charge of silver surface transfers to the pi* orbital of CN bond via S-Ag bond. Consequently, the CN bond is weakened, and the frequency of nu(CN) shifts to lower frequencies. Density functional theory (DFT) calculations further confirm the experimental results that the charge transfer is from PPh3 to silver surface rather than reversely. The information obtained from the adsorption of PPh3 on silver by SERS may be helpful to understand the mechanism of heterogeneous catalysis involving phosphine ligands coordinated on transition-metal surfaces.
关键词[WOS]: SURFACE-ENHANCED RAMAN ;  INFRA-RED SPECTRA ;  PHOSPHORUS LIGANDS ;  RH/SIO2 CATALYST ;  GOLD ELECTRODES ;  PPH3 LIGAND ;  SCATTERING ;  COMPLEXES ;  PARTICLES ;  NANOPARTICLES
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000247215200035
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/99691
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China

Recommended Citation:
Hu, Gengshen,Feng, Zhaochi,Han, Difei,et al. Charge transfer between triphenyl phosphine and colloidal silver: A SERS study combined with DFT calculations[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2007,111(24):8632-8637.
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