First-principles and microkinetic simulation studies of CO2 hydrogenation mechanism and active site on MoS2 catalyst

Molybdenum disulphide (MoS2) has attracted much attention as a promising non-precious metal catalyst for CO2 hydrogenation to energy-rich commodities. However, the exact reaction mechanism and active site on the MoS2 catalyst are still a matter of debate. Using density functional theory (DFT) calculations and microkinetic modeling, we study the competitive pathways leading to the formation of CO, methane and methanol at the S edge site in MoS2 catalyst, and the results are compared to those on the Mo edge and MoS2(0 0 1) in our previous work. It is found that CO is exclusively produced through redox mechanism on the S edge at 580-780 K, 1 bar and H2/CO2 ratio of 1, with the rate determining step of C-O bond scission in CO2. The rate of CO formation follows the order of Mo edge > S edge > MoS2(0 0 1), suggesting the Mo edge as the likely active site on the MoS2 catalyst. This work offers a mechanistic understanding toward CO2 hydrogenation on the MoS2 catalyst at the atomic level, and the insights gained can be used to design improved catalysts for the CO2 and CO hydrogenation and other important reactions of technological interest.

Automated summary

Molybdenum disulfide (MoS2) is a promising non-precious metal catalyst for CO2 hydrogenation, but the exact reaction mechanism and active site are still debated. This study investigates the competitive pathways for CO, methane, and methanol formation on the S edge site of MoS2 catalyst using DFT calculations and microkinetic modeling. It reveals that CO is exclusively produced through a redox mechanism on the S edge, with Mo edge as the likely active site. This work provides a mechanistic understanding of CO2 hydrogenation on MoS2 catalyst, and can aid in designing improved catalysts for important technological reactions.