Gas-phase reactions of tungsten carbide and nitride cluster cations, W_nC_m⁺ (n = 1–5, m ≤ 5) and W_nN_m⁺ (n = 1–6, m ≤ 2), with methane are investigated at near thermal energies. Most of the clusters react readily with CH₄ to form W_nC_m+1H₂⁺ or W_nN_mCH₂⁺ under single collision conditions, in contrast to the almost no reactivity of pure tungsten clusters. This result indicates that the introduction of carbon or nitrogen atoms can enhance the reactivity of tungsten clusters toward the CH₄ dehydrogenation. In addition, the formation and the release of an ethylene molecule are strongly suggested in the reaction of WC⁺ with CH₄ as a minor reaction channel. Nearly all the nitride cluster cations, W_nN_m⁺ (n ≥ 2), exhibit higher reactivity than their corresponding carbides, W_nC_m⁺, whereas WN⁺ is less reactive than WC⁺. Furthermore, the multiple collision reactions of the highly reactive tungsten nitride species such as WN⁺ and W₄N⁺ lead to the formation of W_nN_mC_xH_2x⁺ (x = 2, 3), which shows that the dehydrogenation of more than one CH₄ molecule occurs.

中文翻译：

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碳化钨和氮化物簇阳离子活化甲烷。

钨碳化物和氮化物簇的阳离子，W的气相反应_Ñ Ç_米⁺（Ñ = 1-5，米≤5）和W _Ñ Ñ_米⁺（Ñ = 1-6，米≤2）中，用甲烷进行了研究在接近热能的情况下。大多数簇容易与CH ₄反应形成W _n C _{m +1} H ₂ ⁺或W _n N _m CH ₂ ⁺在单次碰撞条件下，与纯钨簇几乎没有反应性相反。该结果表明，碳或氮原子的引入可以增强钨簇对CH ₄脱氢的反应性。另外，强烈建议在WC ⁺与CH ₄作为次要反应通道的反应中乙烯分子的形成和释放。几乎所有的氮化物簇的阳离子，W _Ñ Ñ_米⁺（Ñ ≥2），表现出比其相应的碳化物，W更高的反应性_Ñ Ç_米⁺，而WN ⁺比WC更少的反应性⁺。此外，高反应性氮化钨物种（例如WN ⁺和W ₄ N ^+）的多次碰撞反应导致形成W _n N _m C _x H _{2 x} ⁺（x = 2，3），这表明脱氢一个以上的CH ₄分子发生了。