Single-Atom X/g-C3N4(X = Au1, Pd1, and Ru1) Catalysts for Acetylene Hydrochlorination: A Density Functional Theory Study

Abstract

The mechanisms of the single-atom X/g-C3N4(X = Au1, Pd1, and Ru1) catalysts for the acetylene hydrochlorination reaction were systematically investigated using the density functional theory (DFT) B3LYP method. The density functional dispersion correction obtained by the DFT-D3 method was taken into account. During the reaction, C2H2 and HCl were well activated and the analysis of the adsorption energy demonstrated the adsorption performance of C2H2 is better than that of HCl. The catalytic mechanisms of the three catalysts consist of one intermediate and two transition states. Moreover, our results showed that the three single-atom catalysts improve the catalytic activity of the reaction to different degrees. The calculated energy barrier declines in the order of Pd1/g-C3N4 > Ru1/g-C3N4 > Au1/g-C3N4, and the energy barrier for the Au1/g-C3N4 catalyst was only 13.66 kcal/mol, proving that single-atom Au1/g-C3N4 may be a potential catalyst for hydrochlorination of acetylene to vinyl chloride.

First-principles calculations for determining the mechanism of the photocatalytic selective oxidation of toluene to benzaldehyde on the g-C3N4 catalyst

“…44 Thus, in order to simulate the maximum active space, we chose three adjacent tri- s -triazine units as the initial structure for the study and optimized it. 33 Hydrogen atoms saturated the dangling bonds of the boundary atoms to simplify the cluster model, thus the surface edges were not taken into account. By optimizing the cluster model, two configurations, namely corrugated and planar, were obtained, as shown in Fig.…”

“…Then, the obtained supercell was imported into GaussView software, and the redundant atoms were deleted to obtain three adjacent tri-s-triazine units, in which the six N atoms at the boundary have hanging bonds, saturated with H atoms, according to a model that has been reported in other articles. 33,34 The atomic coordinates for the calculated structure of the g-C 3 N 4 cluster are shown in Table S1 (ESI †). Moreover, the lowest energy structure for g-C 3 N 4 was a structure with M = 1 spin multiplicity.…”

Polymeric micelles with chiral diamine-Ru(II) catalysts for asymmetric transfer hydrogenation of ketones in water

“…Our group has conducted extensive study on micelle catalysis, different organocatalyst [29][30][31] and organometallic catalyst [32,33] Grubbs catalyst was synthesized according to the previously reported method [34]. Exo-5-norbornene-2-carboxylic acid was synthesized according to our previous report [35].…”

Nitrogen-doped porous carbon from biomass with superior catalytic performance for acetylene hydrochlorination

“…Furthermore, they demonstrated that pyridinic N and pyrrolic N maybe the active sites for hydrogen chloride and acetylene, and pore character effect on catalysis by experiment and DFT. 17,19,20,[22][23][24][25] Li and coworkers also reported many works of mercury-free catalyst, including nitrogen-doped carbon catalyst for acetylene hydrochlorination. 26 Jiang and co-workers reported the catalytic coupling reaction of acetylene and ethylene dichloride to synthesize VCM using nitrogen-doped activated carbon (AC) as the catalyst.…”