arXiv subjects

Xiaoqian Yao

Publications and source records attributed to Xiaoqian Yao.

2 recordsLinked to original sources

arXiv2021

The effects of halide anions on the electroreduction of CO2 to C2H4: a density functional theory study

The halide anions present in the electrolyte gradually improves the Faradaic efficiencies (FEs) of the multi-hydrocarbon (C2+) products for the electrochemical reduction of CO2 over copper (Cu) catalysts in the order of F- < Cl- < Br- < I-. However, the mechanism behind the increased yield of C2+ products with the addition of halide anions still remains indistinct. In this study, we analysed the mechanism by investigating the electronic structures and computing the relative free energies of intermediates formed from CO2 to C2H4 on the Cu (100) facet based on density functional theory (DFT) calculations. The results show that formyl *CHO species from the hydrogenation reaction of the adsorbed *CO acts as the key intermediate, and the C-C coupling reaction occurs preferentially between the *CHO and *CO with the formation of a *CHO-CO intermediate. Subsequently, the free-energy pathway of C2H4 formation has been proposed, and we found that the presence of halide anions significantly decreases the free energy of the *CHOCH intermediate, and enhances the desorption capacity of C2H4 in the order of F- < Cl- < Br- < I-. Lastly, the obtained results are rationalized by the Bader charge analysis.

physics.chem-ph↗

arXiv2021

The effects of ionic liquids on the thermodynamics of H2 activation by frustrated Lewis pairs: a density functional theory study

Nowadays, hydrogen activation by frustrated Lewis pairs (FLPs) and their applications have been demonstrated to be one of emerge research topics in the field of catalysis. Previous studies have shown that the thermodynamics of these reaction is determined by electronic structures of FLPs and solvents. Herein, we investigated the systems consisting of typical FLPs and ionic liquids (ILs), which are well known by their large number of types and excellent solvent effects. The density functional theory (DFT) calculations were performed to study the thermodynamics for H2 activation by both inter- and intra-molecular FLPs, as well as the individual components. The results show that the computed overall Gibbs free energies in ILs are more negative than that computed in toluene. Through the thermodynamics partitioning, we find that ILs favor the H-H cleavage elemental step, while disfavored the elemental steps of proton attachment, hydride attachment and zwitterionic stabilization. Moreover, the results show that these effects are strongly dependent on the type of FLPs, where intra-molecular FLPs are more effected compared to the inter-molecular FLPs.

physics.chem-ph↗