Adsorption of methane as well as co-adsorption of methane and O2 on NirAl2O3 catalyst have been studied by in situFT-IR spectroscopy. The reaction start temperature measurements indicate that the methane partial oxidation occurs at2308C. As the reduced NirAl2O3 was exposed to pure CH4, two bands for adsorbed methane were observed at 3005 and2998 cmy1, respectively, which was confirmed by the appearance of two bands at 2242 and 2237 cmy1 when CD4 wasused. During temperature programmed _TP. dynamic process _in the presence of CH4., the intensities of the bands at 3005and 2998 cmy1 increased with increase in temperature, indicating that the amount of adsorbed methane increases withincreasing temperature, which is indicative of chemisorption of methane. During TP dynamic process _in the co-presence ofCH4 and O2., two forms of chemisorbed methane are observed. The amount of chemisorbed methane increased withincreasing temperature. At 2508C, the intensity of the band at 3015 cmy1 for gaseous methane decreased remarkably and atthe same time, CO, H2, CO2 and H2O were detected in the gas phase, indicating that the partial oxidation of CH4 occurs,which is in good agreement with the reaction start temperature observed above. These results suggest that the dissociation ofchemisorbed methane in the participation of chemisorbed oxygen is a key step for methane partial oxidation.

The adsorption of H2 as well as coadsorption of H2 and CO on Rh2Co2/A1203 catalyst has beenstudied using in situ FTIR dynamic method. The band at 1959 cm-1 for Rh--H vibration on Rh2Co2/A1203(w=3%) was observed and increased in intensity without shift to low wavenumber as Hz coverage increase. In the dynamic process of CO adsorption on Rh2Coz/AI203 preadsorbing H2-TP(in H2 and CO), the bands for the gem-dicarbonyl species, the linear CO species and the bridge earbonyl species were lost and the bands for carbonyl hydrides were observed at 293K. At about 473K, the C-O bond of rhodium carbonyl hydrides starts to break down and CO hydrogenation reaction occurs. It can be concluded that the scission of C-O bond under the conditions of CO hydrogenation is via rhodium carbonyl hydrides.

The forms of chemiso rption of H2 over Rh-V

本文报导了以高眭能稀土储氧材料为基础、制各出高眭能高耐久眭的Pt-Rh型三效催化剂，经过8万公里快速老化实验，催化剂仍保持高活眭和高稳定眭。

A new monolithic Ni/CeO2-ZrO2/γ-Al2O3 catalyst for combined partial oxidation andCO2 reforming of methane was prepared. The result shows that the addition of O2 to the feed canimprove the activity of the catalyst and adjust the H2/CO ratio of the productive gases.

以钛酸四丁酯为原料，采用溶胶-凝胶法制备了二氧化钛，用发光材料Sr2CeO4负载二氧化钛，经450℃焙烧得到不同负载量的光催化剂。以苯为模拟气体，在静态反应装置中考察了该催化剂对苯氧化的催化性能，结果表明，二氧化钛负载在Sr2CeO4上能显著提高对气相苯的光催化降解性能，二氧化钛负载量为110%时催化剂活性最高，在反应的6h内未观察到催化剂有失活的现象。

以Ce0.25Zr0.50Mn0.25O2（OSM）和YSZ2Al2O3（Y2O3，ZrO2稳定的γ2Al2O3）为载体，制备了Co/OSM和Co/YSZ2Al2O3整体式催化剂，以及不同Co/OSM:Co/YSZ2Al2O3 比例的Co/OSM+Co/YSZ2Al2O3 整体式催化剂。研究了上述催化剂的甲烷催化燃烧性能，并利用XRD和H2-TPR对催化剂进行了表征。XRD结果表明，在OSM和YSZ-Al2O3上Co均以高分散形式存在。H2-TPR 结果表明，Co/OSM+Co/YSZ-Al2O3样品的可还原性随着Co/OSM含量的增加而提高，表现出可调节的还原性能。Co/OSM的甲烷燃烧催化活性高于Co/YSZ-Al2O3，Co/OSM Co/YSZ-Al2O3表现出协同作用和高活性。

The reactions of (1) CH4 +MgO→MgOH¥ +CH3¥ and (2) CH4 + MgO→Mg+CH3OH have beenstudied on the singlet spin state potential energy surface at the MP2/6-311+G(2d,2p) level. These two reactionchannels, both involving intermediates and transition states, have been rationalized by the structures of thespecies involved, natural bond orbital (NBO), and vibrational frequency analysis. We have considered twoinitial interacting models between CH4 and MgO: a collinear C-H approach to the O end of the MgOforming the MgOCH4 complex with C3V symmetry and three hydrogen atoms of the methane point to the Mgend of the MgO forming the OMgCH4 complex with C1 symmetry. The calculations predict that reactions 1and 2 are exothermic by 39.8 and 86.5 kJ mol-1, respectively. Also, the former reaction proceeds more easilythan the latter, and the complex HOMgCH3 is energetically preferred in the reaction of MgO + CH4.

用溶胶凝胶法制备了不同锰含量的Ce-Zr-Mn-O 固溶体，样品在老化前后均用XRD、TPR 表征，并测定其储氧性能。结果表明锰含量对该储氧材料（OSM）的储氧性能有很大的影响: 样品的储氧量（OSC）老化前随着Mn 含量的增加而增加；老化后则先增加而后又降低，以Mn 含量20%为最佳。以不同比例的OSM（含20%锰）YSZ2Al2O3 为载体制备了一系列Fe、Co、Mn三组分氧化物的整体式催化剂，考察了它们的甲烷催化燃烧活性。结果表明老化前后，Fe-Co-Mn/OSM+YSZ-Al2O3（其中OSM 和YSZ-Al2O3质量比为1:1）活性明显高于Fe-Co-Mn/YSZ-Al2O3，且具有可与贵金属催化剂相比美的特性-较低的起燃温度、很窄的完全反应温度区间，同时兼有较好的热稳定性，有望成为实用的甲烷燃烧催化剂。

The reactions between Ni (d101S) and CH4 have been carried out at the B3LYP/6-311+G(2d, 2p) and B3LYP/6-311++G(3df,2p) theoretical levels. The reaction path in which the intermediates transfer from one to another viatransition state is rationalized by their structures and natural bond orbital analysis. The reactions of Ni＋CH4→NiCH2＋H2, Ni＋CH4→NiCH3+H and Ni+CH4→NiH+CH3 are predicted to be endothermic, and the reactionNi+CH4→NiH+CH3 is the easiest to occur.