Theoretical design of ruthenium single-atom catalysts with different substrates for acetylene hydrochlorination

Ruthenium-based catalysts exhibit excellent catalyst activity in the acetylene hydrochlorination reaction and tend to be a good substitute for mercury-based catalysts due to their cheaper price among the precious metal catalysts. In this work, spin-polarized density functional theory (DFT) calculations were carried out to investigate the properties of the ruthenium single-atom catalysts supported on six different substrates (four pyridine nitrogen-doped carbon, four or three pyrrole nitrogen-doped carbon, C2N, CN and g-C3N4), and the reaction mechanisms of acetylene hydrochlorination catalyzed by them at 453 K. According to the results of calculations, it could be found that the reaction had the lowest free energy barrier of 16.83 kcal/mol on the Ru@4 x N6 (pyridine nitrogen-doped carbon), while it had the highest free energy barrier of 49.06 kcal/mol on the Ru@g-C3N4. This work will provide a theoretical support for the design of ruthenium single-atom catalysts for acetylene hydrochlorination reaction.