Hirabayashi Shinichi, Okawa Ryuji, Ichihashi Masahiko, Kawazoe Yoshiyuki, Kondow Tamotsu
East Tokyo Laboratory, Genesis Research Institute, Inc., 717-86 Futamata, Ichikawa, Chiba 272-0001, Japan.
J Chem Phys. 2009 Apr 28;130(16):164304. doi: 10.1063/1.3121503.
Structures of methanol molecules chemisorbed on cobalt cluster ions, Co(n)(+) (n=2-6), were investigated by infrared photodissociation (IR-PD) spectroscopy in the wavenumber range of 3400-4000 cm(-1). All the IR-PD spectra measured exhibit an intense peak in the region of the OH stretching vibration. In the IR-PD spectra of Co(2)(+)(CH(3)OH)(2,3) and Co(3)(+)(CH(3)OH)(3), weak peaks were observed additionally in the vicinity of 3000 cm(-1), being assignable to the CH stretching vibration. The comparison of the experimental results with the calculated ones leads us to conclude that (1) molecularly chemisorbed species, Co(n)(+)(CH(3)OH)(m) (m=1-3), and dissociatively chemisorbed species, Co(n)(+)(CH(3)OH)(m-1)(CH(3))(OH), are dominant and (2) the methanol dehydrogenation proceeds via an intermediate, Co(n)(+)(CH(3))(OH).
通过红外光解离（IR-PD）光谱在3400 - 4000 cm⁻¹波数范围内研究了化学吸附在钴簇离子Co(n)⁺（n = 2 - 6）上的甲醇分子结构。所有测量的IR-PD光谱在OH伸缩振动区域都有一个强峰。在Co(2)⁺(CH₃OH)₂,₃和Co(3)⁺(CH₃OH)₃的IR-PD光谱中，在3000 cm⁻¹附近还观察到弱峰，可归因于CH伸缩振动。将实验结果与计算结果进行比较，我们得出以下结论：（1）分子化学吸附物种Co(n)⁺(CH₃OH)ₘ（m = 1 - 3）和解离化学吸附物种Co(n)⁺(CH₃OH)ₘ₋₁(CH₃)(OH)占主导地位；（2）甲醇脱氢通过中间体Co(n)⁺(CH₃)(OH)进行。
