Unraveling the Synergistic Reaction and the Deactivation Mechanism for the Catalytic Degradation of Double Components of Sulfur-Containing VOCs over ZSM-5-Based Materials

Rui Tian; Jichang Lu; Zhizhi Xu; Wenjun Zhang; Jiangping Liu; Langlang Wang; Yibing Xie; Yutong Zhao; Xiaohua Cao; Yongming Luo

doi:10.1021/acs.est.2c04033

Unraveling the Synergistic Reaction and the Deactivation Mechanism for the Catalytic Degradation of Double Components of Sulfur-Containing VOCs over ZSM-5-Based Materials

Environ Sci Technol. 2022 Oct 4. doi: 10.1021/acs.est.2c04033. Online ahead of print.

Authors

Rui Tian^{1

2

3}, Jichang Lu^{1

4

2

3}, Zhizhi Xu^{1

4

2

3}, Wenjun Zhang^{1

2

3}, Jiangping Liu^{1

2

3}, Langlang Wang¹, Yibing Xie¹, Yutong Zhao^{1

2

3}, Xiaohua Cao^{1

4

2

3}, Yongming Luo^{1

4

2

3}

Affiliations

¹ Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming650500, P. R. China.
² The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, Kunming650500, P. R. China.
³ The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming650500, P. R. China.
⁴ Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming650500, P. R. China.

PMID: 36196013
DOI: 10.1021/acs.est.2c04033

Abstract

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.

Keywords: carbon and sulfur deposition; competitive adsorption; deactivation mechanism; sulfur-containing VOCs; synergistic catalytic decomposition.