The competitive adsorption behavior, the synergistic catalytic reaction, and deactivation mechanisms under double components of sulfur-containing volatile organic compounds (VOCs) are a bridge to solve their actual pollution problems. However, they are still unknown. Herein, simultaneous catalytic decomposition of methyl mercaptan (CH₃SH) and ethyl mercaptan (C₂H₅SH) is investigated over lanthanum (La)-modified ZSM-5, and kinetic and thermodynamic results confirm a great difference in the adsorption property and catalytic transformation behavior. Meanwhile, the new synergistic reaction and deactivation mechanisms are revealed at the molecular level by combining with in situ diffuse reflectance infrared spectroscopy (in situ DRIFTS) and density functional theory (DFT) calculations. The CH₃CH₂* and SH* groups are presented in decomposing C₂H₅SH, while the new species of CH₂*, active H* and S*, instead of CH₃* and SH*, are proved as the key elementary groups in decomposing CH₃SH. The competitive recombining of SH* in C₂H₅SH with highly active H* in dimethyl sulfide (CH₃SCH₃), an intermediate in decomposing CH₃SH, would aggravate the deposition of carbon and sulfur. La/ZSM-5 exhibits potential environmental application due to the excellent stability of 200 h and water resistance. This work gives an understanding of the adsorption, catalysis, reaction, and deactivation mechanisms for decomposing double components of sulfur-containing VOCs.

中文翻译：

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揭示 ZSM-5 基材料催化降解含硫 VOC 双组分的协同反应和失活机制

含硫挥发性有机化合物（VOCs）双组分下的竞争吸附行为、协同催化反应和失活机制是解决其实际污染问题的桥梁。然而，他们仍然是未知数。在此，研究了在镧 (La) 改性的 ZSM-5 上同时催化分解甲硫醇 (CH ₃ SH) 和乙硫醇 (C ₂ H ₅ SH)，动力学和热力学结果证实吸附性能和催化转化行为。同时，结合原位漫反射红外光谱（in situDRIFTS）和密度泛函理论（DFT）计算。CH ₃ CH ₂ * 和SH*基团在分解C ₂ H ₅ SH时出现，而CH ₂ * 新物种活性H*和S*代替CH ₃ *和SH*被证明是关键分解 CH ₃ SH 时的基本基团。_{C 2} H ₅ SH 中的 SH* 与二甲基硫醚 (CH ₃ SCH ₃ ) 中的高活性 H*的竞争性重组，一种分解 CH _{3的中间体}SH，会加剧碳和硫的沉积。La/ZSM-5 具有出色的 200 h 稳定性和耐水性，具有潜在的环境应用潜力。这项工作有助于了解分解含硫 VOC 双组分的吸附、催化、反应和失活机制。