COx hydrogenation to methanol and other hydrocarbons under mild conditions with Mo3S4@ZSM-5

• Published in: Nature communications Vol. 14; no. 1; p. 513
• Main Authors: Liu, Gui, Liu, Pengfei, Meng, Deming, Zhao, Taotao, Qian, Xiaofeng, He, Qiang, Guo, Xuefeng, Qi, Jizhen, Peng, Luming, Xue, Nianhua, Zhu, Yan, Ma, Jingyuan, Wang, Qiang, Liu, Xi, Chen, Liwei, Ding, Weiping
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 31.01.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/133; 140/146; 140/58; 147/143; 639/301/299/1013; 639/638/675; 639/638/77/887; Cages; Carbon dioxide; Carbon monoxide; Catalysts; Catalytic converters; Clusters; Degeneration; Fixed bed reactors; Fixed beds; Humanities and Social Sciences; Hydrocarbons; Hydrogenation; Ions; Methanol; Molecular sieves; Molybdenum; multidisciplinary; Science; Science (multidisciplinary); Selectivity
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-36259-9

The hydrogenation of CO 2 or CO to single organic product has received widespread attentions. Here we show a highly efficient and selective catalyst, Mo 3 S 4 @ions-ZSM-5, with molybdenum sulfide clusters ([Mo 3 S 4 ] n+ ) confined in zeolitic cages of ZSM-5 molecular sieve for the reactions. Using continuous fixed bed reactor, for CO 2 hydrogenation to methanol, the catalyst Mo 3 S 4 @NaZSM-5 shows methanol selectivity larger than 98% at 10.2% of carbon dioxide conversion at 180 °C and maintains the catalytic performance without any degeneration during continuous reaction of 1000 h. For CO hydrogenation, the catalyst Mo 3 S 4 @HZSM-5 exhibits a selectivity to C 2 and C 3 hydrocarbons stably larger than 98% in organics at 260 °C. The structure of the catalysts and the mechanism of CO x hydrogenation over the catalysts are fully characterized experimentally and theorectically. Based on the results, we envision that the Mo 3 S 4 @ions-ZSM-5 catalysts display the importance of active clusters surrounded by permeable materials as mesocatalysts for discovery of new reactions. A series of materials containing Mo-S clusters confined in zeolitic cages of ZSM-5 are reported and shown to be efficient for CO 2 or CO hydrogenation with >98% selectivity to methanol, stable over 1000 h, or C 2 and C 3 hydrocarbons, stable over 100 h.