过渡金属碳化物作为一种催化新材料显示了其独特的性能，在石油馏份的HDS、HDN、加氢和脱氢反应、烃的异构化和芳构化、甲烷转化、F-T合成和电催化等反应中都表现出了优良的催化性能。本文综述了国内外关于钼、钨碳化物的制备方法以及在上述反应中的应用研究进展。

考察了反应温度、气体空速和进料中CH4∶O2比值对Mo2C/Al2O3催化的POM反应制合成气的影响。结果发现较高的温度具有较高的甲烷转化率、CO和H2的选择性；而在较低的温度下，对CO的选择性比对H2的影响更大。反应气体的空速较小时对于甲烷的转化率、CO和H2的选择性是有利的；而在较高的气体空速下，氢气的选择性则更低。进料中CH4∶O2 比值稍高于2∶1时有利于获得高的甲烷转化率、CO和H2的选择性，并且还可以增加催化剂的稳定性。当CH4∶O 2比值低于2∶1时，甲烷转化率、CO和H2选择性随反应的进行急剧下降，而当此比值调整到高于2∶1时，转化率和选择性都可以得到恢复。

A series of Na-W-Mn/SiO2 catalysts with different sodium, tungsten, and manganese contents (wt.%) were prepared and their catalytic performance for the oxidative coupling of methane (OCM) was evaluated in a continuous micro-reactor. The structural properties of the catalysts have been characterised using XPS, laser Raman spectroscopy (LRS), and X-ray diffraction (XRD). The results show that the catalysts containing Na, W, and Mn between the range of 0.4-2.3, 2.2-8.9, and 0.5-3.0 wt.%, respectively, had high CH4 conversion and high selectivity to C2 hydrocarbons in the OCM reaction. The addition of sodium to the catalyst is believed to bring about the migration of manganese to the catalyst surface, as both elements are found in high concentrations in this area. CH4 conversion and the selectivity to C2H4 are closely related to the surface Mn concentration of the catalysts. Both Na-O-Mn and Na-O-W act as the active centres of the catalysts for the oxidative coupling of methane. The catalyst surface is mainly covered with Na and O, while the Mn and W are present in the sub-surface of the catalyst. There is a synergic effect of sodium, tungsten, and manganese components, and the Na2W2O7 crystalline phase is active for the oxidative coupling of methane.

Alumina-supported molybdenum carbide and its modifier with small amounts of nickel were evaluated and characterized. The evaluation results showed that a nickel-doped carbide catalyst exhibited a much higher conversion of methane and selectivity to CO and H2for the partial oxidation of methane (POM) to syngas. Also, the addition of a small amount of nickel resulted in significant improvement of catalysis stability. Characterization by temperature programmed surface reaction (TPSR) indicated that the addition of nickel promoted the carburization of molybdenum oxide. Especially under the conditions of the POM to syngas, this promotion resulted in more active phases being held. The nickel doped catalyst had small particles, larger specific area and greater ability to resist sintering. All these improved the catalytic stability. The other characterizations by XRD, XPS, SEM as well as BET surface area measurement also confirmed these promotions of nickel. In addition, the doped nickel made possible the increase of the intrinsic activity of catalytic centers over molybdenum carbide catalyst.

制备了多组分Na、W、Mn/SiO2催化剂，在ITD（Ion Trap Detector）装置上进行了催化剂表面晶格氧脱附前后的甲烷恒温脉冲反应（CH4-CTPR）。研究结果表明，Na-W/SiO2催化剂表面晶格氧，具有较高的CH4转化率和C2烃选择性，并对C2H6 的生成起着重要的作用；Na-M n/SiO2催化剂表面晶格氧，也具有较高的CH4转化率和C2烃选择性，但对C2H6 的形成有一定的诱导期；W-M n/SiO2催化剂表面晶格氧，对CH4的转化和CO2的生成具有很高初活性，但对C2烃的选择性较低；Na-W-M n/SiO2催化剂表面晶格氧，具有很高的CH4转化率和C2烃定向选择性，这是由于Na、W、M n各组分协同作用的结果