Detection, role and utilization of excited molecules in catalytic reaction by means of IR chemiluminescence

(1)通过测量振动激发产物分子（1-1）CO+O_2在Pd（110）上的催化反应的红外辐射，提出了利用红外辐射强度分析Pd（111）的方法，并测量了振动温度随表面温度升高的变化。（1-2） CO+NO反应对Pd（110）、Pd（111）的影响首次发现CO+NO反应的活性具有较大的结构敏感性。NO在Pd（111）上不发生解离，由于NO的解离受到限制，NO的新生氧在Pd（110）上形成。（1 ~ 3） CO+0_2在Pt（110）上反应，Pt（111）在Pt（110）上的活度高于Pt（111）。由于在Pt（110）上将（l × l）重构为（1 × 2），观察到振动温度的变化。(2)利用可加热和种子分子束技术直接催化CH_4和C_2H_6的部分氧化（2-1）甲烷分子束的能量活化促进作用：在Pt上的CH_4+O_2稳态反应中，激发甲烷选择性地生成合成气co +H_2（特别是H_2）。反应也通过还原O_2在Rh上发生。（2-2）甲烷和乙烷在Pt和rh2上催化偏反应中的比较研究根据反应阶数测量的结果，一种可能的解释是，能量活化的甲烷和乙烷与吸附的氧反应产生甲氧基和乙氧基物质，这两种物质被认为是氢生成的前体。

(1) Dynamics of catalytic reactions by measurement of IR emission of the vibrationally-excited product molecules(1-1) CO+O_2 reaction on Pd (110), Pd (111)Analysis method using intensities of IR emission was proposed, and changes in vibrational temperatures were measured with increasing surface temperature.(1-2) CO+NO reaction on Pd (110), Pd (111)Large structure-sensitivity in the activity of the CO+NO reaction was found for the first time. NO Dissociation does not take place on Pd (111), and nascent oxygen from NO is formed on Pd (110) because NO dissociation is limited.(1-3) CO+0_2 reaction on Pt (110), Pt (111)Activity was higher on Pt (110) than on Pt (111). Changes in vibrational temperatures were observed due to the reconstruction of (l x l) into (1 x 2) on Pt (110).(2) Direct catalytic partial oxidation of CH_4 and C_2H_6 using heatable and seeded molecular beam technique(2-1) The promoting effect of energetic activation of a methane molecular beam: production of syngasCO+H_2 (in particular H_2) were produced selectively during steady-state CH_4+O_2 reaction on Pt by exciting methane. The reaction also takes place on Rh by reducing O_2.(2-2) Comparative study between methane and ethane in the catalytic paratial reaction on Pt and RhBased on the results of the reaction order measurements one possible explanation for the promotion is that energetically activated methane and ethane react with adsorbed oxygen and produce methoxy and ethoxy species, which are regarded as precursors for hydrogen formation.