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环氧乙烷(EtO)在Au(211)阶梯表面吸附的程序升温脱附(TPD)和傅里叶变换红外反射吸收光谱(FT-IRAS)研究

TPD and FT-IRAS investigation of ethylene oxide (EtO) adsorption on a Au(211) stepped surface.

作者信息

Kim Jooho, Koel Bruce E

机构信息

Department of Chemistry, University of Southern California, Los Angeles, CA 90089-0482, USA.

出版信息

Langmuir. 2005 Apr 26;21(9):3886-91. doi: 10.1021/la0480639.

Abstract

Adsorption of ethylene oxide, CH(2)CH(2)O (EtO), on a Au(211) stepped surface was studied by temperature programmed desorption (TPD) and Fourier transform infrared reflection-absorption spectroscopy (FT-IRAS). Ethylene oxide was completely reversibly adsorbed, and desorbed molecularly during TPD following adsorption on Au(211) at 85 K. EtO TPD peaks appeared at 115 K from the multilayer film and 140 and 170 K from the monolayer. Desorption at 140 K was attributed to EtO desorption from terrace sites, and that at 170 K to EtO desorption from step sites. Desorption activation energies and corresponding adsorption energies were estimated to be 8.4 and 10.3 kcal mol(-1), respectively. The EtO ring (C(2)O) deformation band appeared in IRAS at 865 cm(-1) for EtO in multilayer films and when adsorbed in the monolayer at terrace sites. The stronger chemisorption bonding of EtO at Au step sites slightly weakens the bonding within the molecule and causes a small red-shift of this band to 850 cm(-1) for adsorption at step sites. EtO presumably binds via the oxygen atom to the surface, and observation of the EtO-ring absorption band in IRAS establishes that the molecular ring plane of EtO adsorbed at step and terrace sites is nearly upright with respect to the crystal surface plane.

摘要

通过程序升温脱附(TPD)和傅里叶变换红外反射吸收光谱(FT-IRAS)研究了环氧乙烷(CH₂CH₂O,EtO)在Au(211)阶梯表面上的吸附。环氧乙烷完全可逆吸附,在85K吸附于Au(211)后,在TPD过程中以分子形式脱附。EtO的TPD峰在115K处出现于多层膜,在140K和170K处出现于单层膜。140K的脱附归因于EtO从平台位点的脱附,170K的脱附归因于EtO从阶梯位点的脱附。脱附活化能和相应的吸附能估计分别为8.4和10.3 kcal mol⁻¹。对于多层膜中的EtO以及吸附在平台位点的单层膜中的EtO,EtO环(C₂O)变形带出现在IRAS的865 cm⁻¹处。EtO在Au阶梯位点的更强化学吸附键合会稍微削弱分子内的键合,并导致该带在阶梯位点吸附时出现小的红移至850 cm⁻¹。EtO大概通过氧原子与表面结合,并且在IRAS中观察到EtO环吸收带表明,吸附在阶梯和平台位点的EtO分子环平面相对于晶体表面平面几乎是直立的。

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