Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals
The one-step synthesis of sulfur-containing chemicals, methanethiol (CH3SH), from syngas and hydrogen sullfide (H2S) mixtures shows the enormous potential for extending the application of both C1 chemistry and sulfur resource recycling and utilization. However, directionally regulating the reaction...
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Elsevier
2025-04-01
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| Series: | Fuel Processing Technology |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S0378382025000086 |
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| author | ZhiZhi Xu Jian Fang Min Luo Dedong He Dingkai Chen Jichang Lu Yongming Luo |
| author_facet | ZhiZhi Xu Jian Fang Min Luo Dedong He Dingkai Chen Jichang Lu Yongming Luo |
| author_sort | ZhiZhi Xu |
| collection | DOAJ |
| description | The one-step synthesis of sulfur-containing chemicals, methanethiol (CH3SH), from syngas and hydrogen sullfide (H2S) mixtures shows the enormous potential for extending the application of both C1 chemistry and sulfur resource recycling and utilization. However, directionally regulating the reaction pathway for synthesizing target sulfur-containing chemicals remain challenging owing to the presence of multiple reactants and the following various competitive side reactions. Herein, we propose a facile and simple sulfurization procedure-dependent strategies to regulate the Mo-S(O) bond strength of K-MoS2 catalysts for highly selective CO-to-CH3SH catalysis. The activity tests, the characterization results and in situ DRIFTS technique demonstrate that a slower sulfurization heating rate and abundant-reduced sulfurization atmosphere facilitate the formation of K-intercalated 1 T-MoS2 phase, which possesses a weaker Mo-S(O) bond than that of CO bond in CO molecules. This weakened bonding pattern is advantageous to the CO non-dissociative activation to from ⁎COS species, and the further hydrogenation of adsorbed ⁎COS and ⁎CHxS species to main product of CH3SH. Otherwise, the strong bonding of Mo-S(O) bond with CO molecule over K-decorated 2H-MoS2 phase can lead to the breakage of CO bond, promoting the formation of CHx species and the occurrence of methanation side reaction. This strategy could provide the useful guidance for the fine regulation of the main and side reaction pathway for producing important chemicals from carbon and sulfur basic materials. |
| format | Article |
| id | doaj-art-967a7de78d494ff2989a813b30d03cff |
| institution | Kabale University |
| issn | 0378-3820 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Fuel Processing Technology |
| spelling | doaj-art-967a7de78d494ff2989a813b30d03cff2025-02-09T04:59:41ZengElsevierFuel Processing Technology0378-38202025-04-01268108184Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicalsZhiZhi Xu0Jian Fang1Min Luo2Dedong He3Dingkai Chen4Jichang Lu5Yongming Luo6Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR ChinaFaculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR China; Corresponding authors.Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR ChinaFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR ChinaFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR China; Corresponding authors.Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR ChinaFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Key Laboratory of Yunnan Province for Synthesizing Sulfur-containing Fine Chemicals, The Innovation Team for Volatile Organic Compounds Pollutants Control and Resource Utilization of Yunnan Province, The Higher Educational Key Laboratory for Odorous Volatile Organic Compounds Pollutants Control of Yunnan Province, Kunming 650500, PR China; Corresponding authors.The one-step synthesis of sulfur-containing chemicals, methanethiol (CH3SH), from syngas and hydrogen sullfide (H2S) mixtures shows the enormous potential for extending the application of both C1 chemistry and sulfur resource recycling and utilization. However, directionally regulating the reaction pathway for synthesizing target sulfur-containing chemicals remain challenging owing to the presence of multiple reactants and the following various competitive side reactions. Herein, we propose a facile and simple sulfurization procedure-dependent strategies to regulate the Mo-S(O) bond strength of K-MoS2 catalysts for highly selective CO-to-CH3SH catalysis. The activity tests, the characterization results and in situ DRIFTS technique demonstrate that a slower sulfurization heating rate and abundant-reduced sulfurization atmosphere facilitate the formation of K-intercalated 1 T-MoS2 phase, which possesses a weaker Mo-S(O) bond than that of CO bond in CO molecules. This weakened bonding pattern is advantageous to the CO non-dissociative activation to from ⁎COS species, and the further hydrogenation of adsorbed ⁎COS and ⁎CHxS species to main product of CH3SH. Otherwise, the strong bonding of Mo-S(O) bond with CO molecule over K-decorated 2H-MoS2 phase can lead to the breakage of CO bond, promoting the formation of CHx species and the occurrence of methanation side reaction. This strategy could provide the useful guidance for the fine regulation of the main and side reaction pathway for producing important chemicals from carbon and sulfur basic materials.http://www.sciencedirect.com/science/article/pii/S0378382025000086Methyl mercaptanCO/H2/H2SSulfurization atmosphereSulfurization heating rateMo-S(O) bond strength regulation |
| spellingShingle | ZhiZhi Xu Jian Fang Min Luo Dedong He Dingkai Chen Jichang Lu Yongming Luo Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals Fuel Processing Technology Methyl mercaptan CO/H2/H2S Sulfurization atmosphere Sulfurization heating rate Mo-S(O) bond strength regulation |
| title | Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals |
| title_full | Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals |
| title_fullStr | Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals |
| title_full_unstemmed | Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals |
| title_short | Modulating the sulfurization procedure to decrease by-product formation for one-step catalytic synthesis of sulfur-containing chemicals |
| title_sort | modulating the sulfurization procedure to decrease by product formation for one step catalytic synthesis of sulfur containing chemicals |
| topic | Methyl mercaptan CO/H2/H2S Sulfurization atmosphere Sulfurization heating rate Mo-S(O) bond strength regulation |
| url | http://www.sciencedirect.com/science/article/pii/S0378382025000086 |
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