Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study

Abstract

The catalytic mechanism of Ru-based catalysts in the acetylene hydrochlorination reaction has been investigated via the density functional theory (DFT) method. To study the effect of the chlorine coordination number on the catalytic mechanism, Ru3Cl9, Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 clusters were chosen as the catalytic models. Our results show that the energy barrier for acetylene hydrochlorination on Ru3Cl9 was as high as 1.51 eV at 458 K. When the chlorine coordination number decreased, the energy barriers on Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 were 1.29, 0.89, 1.01 and 1.42 eV, respectively. On Ru3Cl9, the H and Cl atoms of HCl were simultaneously added to C2H2 to form C2H3Cl, while the reaction was divided into two steps on Ru3Cl7, Ru3Cl3 and Ru3 clusters. The first step was the addition of H atom of HCl to C2H2 to form C2H3˙, and the second step was the addition of Cl atom to C2H3˙ to form C2H3Cl. The step involving the addition of Cl was the rate-controlling step during the whole reaction. On Ru5Cl7 cluster, there was an additional step before the steps involving the addition of H and Cl: the transfer of H atom from HCl to Ru atom. This step was the rate-controlling step during the reaction of acetylene hydrochlorination on Ru5Cl7 and its energy barrier was the lowest among all the above-mentioned catalytic models. Therefore, the Ru5Cl7 cluster played the most predominant role in acetylene hydrochlorination with the largest reaction rate constant kTST of 10(3).

Efficient and stable Ru(III)-choline chloride catalyst system with low Ru content for non-mercury acetylene hydrochlorination

“…The results of this study show that the activation of HCl is the key to improve the catalyst life in this reaction, which is in agreement with previous studies [7,25,[66][67][68]. However, it remains challenging to enhance the adsorption or activation of HCl because the H-Cl bond is sturdy (428 kJ/mol of bond energy) [69].…”

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

“…It can be concluded that RuCl 3 and BaCl 2 are non-polar molecules (zero dipole moment) with regular plane triangular and linear structure, respectively, while AuCl 3 demonstrates an isosceles triangular structure with a dipole moment of 0.0671 Debye. Other references also confirmed these specific structures [12][13][14][15][16].…”

Pyrrolidone ligand improved Cu‐based catalysts with high performance for acetylene hydrochlorination

“…Among a wide variety of available nonmercuric catalysts, Hutchings and other researchers have found that many metal catalysts, such as Au, [8][9][10] Pd, [11,12] Ru, [13][14][15][16] Cu, [17] and so on, all showed high catalytic activities and could be used as substitutes for HgCl 2 in acetylene hydrochlorination. To meet economic benefits, Cu-based catalysts are definitely becoming a research hotspot, [18] and researchers have been pursuing and aiming to improve the catalytic activity and stability.…”