A DFT Study of Methanol Synthesis from CO2 Hydrogenation on the Pd(111) Surface

• Published in: Catalysis letters 2018-09, Vol.148 (9), p.2935-2944
• Main Authors: Zhang, Minhua, Wu, Yufei, Dou, Maobin, Yu, Yingzhe
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Catalysis; Catalysts; Catalytic converters; Chemistry; Chemistry and Materials Science; Conversion; Density functional theory; Hydrogenation; Industrial Chemistry/Chemical Engineering; Mathematical analysis; Methanol; Organic chemistry; Organometallic Chemistry; Physical Chemistry
• ISSN: 1011-372X; 1572-879X
• DOI: 10.1007/s10562-018-2497-y

During the process of catalytic conversion of CO 2 to valuable chemical products, Pd used as catalysts or modifiers shows promising effect on CO 2 hydrogenation. The mechanism of methanol synthesis from the hydrogenation of CO 2 on the Pd(111) surface was studied using density functional theory calculations in present work. On the Pd(111) surface, CO 2 firstly hydrogenates to HCOO or COOH, each of which then reacts with the surface H atom to form HCOOH. Next, HCOOH dissociates to OH and HCO that will be consecutively hydrogenated to H 2 CO, H 3 CO and H 3 COH. CO is the main side product of CO 2 hydrogenation on the Pd(111) surface with an activation barrier of 1.09 eV. The hydrogenation of HCO species with the surface H atom to form H 2 CO plays as the rate determining step for CO 2 hydrogenation to methanol with the barrier of 0.91 eV. Our calculated results are favorable for the understanding of the mechanism of CO 2 conversion on not only Pd-based catalysts but also Pd modified catalysts. Graphical Abstract The mechanism of methanol synthesis from the hydrogenation of CO 2 on the Pd(111) surface was studied using density functional theory calculations.