利用脉冲 质谱在线分析技术考察了无气相氧条件下负载型金属催化剂上脉冲CH4的反应结果表明 ,对于Rh/SiO2 催化剂 ,不管是氧化态还是还原态 ,除第 1次脉冲生成较多的CO2 外 ,从第 2次脉冲开始 ,只有CO生成 ;对于Ru/SiO2 催化剂 ,无论是氧化态还是还原态 ,每次脉冲均有一定量的CO2 生成 .这可能是由于Rh和Ru两种金属对氧的亲合力不同所致 .甲烷在负载型催化剂表面的活化以及产物的选择性主要受催化剂表面活性氧物种覆盖度的影响 . The results of pulse CH4 reaction on unsupported metal catalyst under non-vapor phase oxygen conditions were investigated by pulsed mass spectrometry (in-line analysis). The results showed that for Rh / SiO2 catalyst, in addition to being oxidized or reduced, , Only CO was formed from the second pulse, and a certain amount of CO 2 was generated in each pulse in the Ru / SiO 2 catalyst, both in an oxidized state and a reduced state, probably due to the affinity between Rh and Ru for oxygen The difference between the two factors is that the activation of methane on the supported catalyst surface and the selectivity of the product are mainly affected by the coverage of the surface active oxygen species of the catalyst.