Despite enormous advances achieved with fundamental understanding and catalyst design in many simple catalytic reactions on surfaces, such attempts are scarce for complex catalytic reactions that involve numerous intermediates and elementary reactions, in addition to the complexity of surface structure and reaction condition. The rational simplicity of reaction process can accelerate the identification of active sites and the simulation of reaction conditions. Using Fischer-Tropsch synthesis as probe reaction, we describe a density functional theory based strategy for 18 possible C<sub>2</sub> intermediates identification. We identify the key intermediates and minimum energy pathways for the first C-C bond formation (carbide vs CO insertion), which is compared with methanation. Based on the rational identification of intermediates, the structure dependence (close packed Co, stepped Co and open Co surfaces) and coverage effect on chain growth mechanism and product selectivity are addressed. Our results rationalize well with the present experimental and theoretical observations, which suggest that the computational procedure can be applied to mechanistic identification and rational catalyst design for complex and important reactions of technological interest.<br/>

Computational intermediates identification and structure dependence of chain growth mechanism and product selectivity in Fischer-Tropsch synthesis on Co catalysts

253rd National Meeting (2017)

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