Design of efficient bifunctional catalysts for direct conversion of syngas into lower olefins via methanol/dimethyl ether intermediatesElectronic supplementary information (ESI) available: Experimental details, interpretation of rate equation from kinetic analysis, supplementary figures and tables. See DOI: 10.1039/c8sc01597j

• Main Authors: Liu, Xiaoliang, Zhou, Wei, Yang, Yudan, Cheng, Kang, Kang, Jincan, Zhang, Lei, Zhang, Guoquan, Min, Xiaojian, Zhang, Qinghong, Wang, Ye
• Format: Article
• Language: English
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c8sc01597j

The direct conversion of syngas into lower olefins is a highly attractive route for the synthesis of lower olefins. The selectivity of lower olefins via the conventional Fischer-Tropsch (FT) synthesis is restricted to ∼60% with high CH 4 selectivity due to the limitation by the Anderson-Schulz-Flory (ASF) distribution. Here, we report the design of bifunctional catalysts for the direct conversion of syngas into lower olefins with selectivity significantly breaking the ASF distribution. The selectivity of C 2 -C 4 olefins reached 87% at a CO conversion of 10% and was sustained at 77% by increasing CO conversion to 29% over a bifunctional catalyst composed of Zn-doped ZrO 2 nanoparticles and zeolite SSZ-13 nanocrystals. The selectivity of CH 4 was lower than 3% at the same time. It is demonstrated that the molar ratio of Zn/Zr, the density of Brønsted acid sites of SSZ-13 and the proximity of the two components play crucial roles in determining CO conversion and lower-olefin selectivity. Our kinetic studies indicate that methanol and dimethyl ether (DME) are key reaction intermediates, and the conversion of syngas to methanol/DME is the rate-determining step over the bifunctional catalyst. Formate and methoxide species have been observed on Zn-doped ZrO 2 surfaces during the activation of CO in H 2 , and the formed methanol/DME are transformed into lower olefins in SSZ-13. Zn-ZrO 2 /SSZ-13 catalyzed direct conversion of syngas into lower olefins via methanol/DME intermediates with 77% selectivity at 29% CO conversion.