CH₄ chlorination with reactive Cl₂ occurs via two competing mechanisms: (i) a free-radical-mediated chain reaction resulting in a statistical, non-selective thermodynamic product distribution including polychloromethanes, or (ii) an electrophilic ionic chlorination affording the more selective formation of a desired monochlorinated product (CH₃Cl) with inhibition of poly-chlorination. Herein, the balance between the two competing pathways was controlled using zeolite acid catalysts containing various cations, of which the cations were introduced to the framework simply by ion-exchange that changes the surface acidities and hence the polarities. This resulted in remarkable changes in CH₃Cl yield depending on the type of the cations. From the reaction data and computational calculations, four physicochemical properties of the catalysts can be proposed as the catalysis descriptors describing the electrophilic chlorination pathway: electron affinity, standard reduction potential, physisorption enthalpy, and natural bond orbital charge. CH₃Cl yield increased proportionally with electron affinity and standard reduction potential due to increased polarizability of Cl₂. In addition, the large physisorption enthalpy to CH₃Cl from the cations on the zeolite surface resulted in a decreased CH₃Cl yield due to the increased probability of poly-chlorination. The natural-bond-orbital charges of the cations in the zeolite framework derived by DFT calculations further suggested that strong electrostatic interaction between CH₃Cl and the cations in the zeolite cluster model could increase the residence time of CH₃Cl on the surface, resulting in the increased production of poly-chloromethanes and decreased CH₃Cl yield.

用反应性Cl ₂进行的CH ₄氯化反应通过两种竞争机制发生：（i）自由基介导的链反应导致统计上的非选择性热力学产物分布，包括聚氯甲烷；或（ii）亲电离子氯化反应，具有更高的选择性形成所需的单氯化产物（CH ₃ Cl），并抑制多氯化反应。在本文中，使用包含各种阳离子的沸石酸催化剂控制两个竞争路径之间的平衡，其中仅通过离子交换将阳离子引入到骨架中，所述离子交换改变了表面酸度并因此改变了极性。这导致CH ₃发生了显着变化Cl的产量取决于阳离子的类型。从反应数据和计算计算中，可以提出催化剂的四种物理化学性质作为描述亲电氯化途径的催化描述子：电子亲和力，标准还原电位，物理吸附焓和自然键轨道电荷。由于Cl _2的极化率增加，CH ₃ Cl的产率与电子亲和力和标准还原电势成比例地增加。另外，沸石表面阳离子对CH ₃ Cl的大的物理吸附焓导致CH ₃减少。由于多氯化的可能性增加，Cl收率提高。通过DFT计算得出的沸石骨架中阳离子的自然键轨道电荷进一步表明，CH ₃ Cl与沸石簇模型中阳离子之间的强静电相互作用可能会增加CH ₃ Cl在表面上的停留时间，从而导致增加了聚氯甲烷的产量，降低了CH ₃ Cl的收率。