Quantum mechanical study of CO2 and CO hydrogenation on Cu(111) surfaces doped with Ga, Mg, and Ti

Abstract

DFT methods were used to analyze metal (M)-doped Cu(111) surfaces to identify surface alloys that could catalyze the hydrogenation of CO2. The adsorption of relevant species for CO2/CO hydrogenation were studied on Cu(111) surfaces doped with Ga, Mg, and Ti. Preferred adsorption sites, geometries, and binding energies for relevant intermediates were determined. A systematic study of the thermochemistry of plausible surface reactions for CO2/CO hydrogenation on Ga/Cu(111), Mg/Cu(111), and Ti/Cu(111) was performed to postulate reaction mechanisms for the synthesis of formic acid, formaldehyde, and methanol. Our results suggest that Ga/Cu(111) and Mg/Cu(111) surfaces might be promising catalysts for the synthesis of methanol from CO2 hydrogenation. CO2 is activated by chemisorption on Mg/Cu(111) and Ti/Cu(111), but the latter surface has a strong interaction with O, which inhibits the last reaction steps and the desorption of the products. Our results demonstrate that the thermochemistry of CO2 hydrogenation for the synthesis of the different products varies drastically depending on the dopant on Cu(111). Furthermore, our results suggest that the formation energies of HCOO, CH2O, CH3O, and HCO are good descriptors for catalyst screening.

Enhanced CO2 Hydrogenation to Methanol on the Mesostructured Cu–ZnO/Al2O3–ZrO2 Catalyst

“…It is well known that CO is an electron-deficient molecule and prefers to adsorb on the surface with high surface electron density, and a strong basic surface usually means a high surface electron density. , Meanwhile, the adsorption of CO on Cu was enhanced due to the strong basic surface, which inhibited the production of CO from the reverse water gas shift and the methanol dissociation in the hydrogenation of CO 2 to methanol and then increased the selectivity to methanol . In addition, the adsorbed CO also reacted with dissociated hydrogen on the Cu surface to methanol . Therefore, the catalyst CZAZ-7 with the strongest surface basicity had the highest methanol selectivity.…”

“…7 In addition, the adsorbed CO also reacted with dissociated hydrogen on the Cu surface to methanol. 36 Therefore, the catalyst CZAZ-7 with the strongest surface basicity had the highest methanol selectivity.…”

Mechanistic Study of Pd–Cu Bimetallic Catalysts for Methanol Synthesis from CO2 Hydrogenation

“…Density functional theory (DFT) calculations have become powerful tools to investigate the theoretical chemical reaction mechanisms of methanol synthesis via the hydrogenation of CO 2 at the atomic level. ,− Significant efforts have focused on clarifying the mechanisms on different metal surfaces, such as Cu, , Cu 29 , Ni, Pd/oxides, and Cu alloys. − The mechanism and selectivity of CO hydrogenation on pure Pd surfaces have been studied . It confirmed that the selectivity of the pure Pd catalysts was toward forming methanol rather than forming methane.…”

Comprehensive Understanding of Bi‐functional Behavior of PNP‐Pincer Complexes Towards the Conversion of CO into Methanol and CO2: A DFT Approach

“…Experimentally, the hydrogenation and hydrolysis of CO without the assistance of any catalyst are difficult to achieve. Thus, a variety of heterogeneous and homogeneous catalytic processes have been adopted till date to convert CO containing gases (syn‐gas and water‐gas) into the aforementioned organic molecules. In 1921, Patart first reported the synthesis of methanol from CO and H 2 .…”

“…reported the hydrogenation of CO mediated by Cu−Ni bimetallic surface from both the experimental as well as theoretical perspectives. Santiago‐Rodriguez et al . investigated the catalytic performance of metal (Ga, Mg and Ti)‐doped Cu(111) surfaces in the hydrogenation of CO 2 and CO employing DFT methods.…”