Asymmetric Sites on the ZnZrOx Catalyst for Promoting Formate Formation and Transformation in CO2 Hydrogenation.
J Am Chem Soc
; 145(23): 12663-12672, 2023 Jun 14.
Article
en En
| MEDLINE
| ID: mdl-37261391
The role of formate species for CO2 hydrogenation is still under debate. Although formate has been frequently observed and commonly proposed as the possible intermediate, there is no definite evidence for the reaction of formate species for methanol production. Here, formate formation and conversion over the ZnZrOx solid solution catalyst are investigated by in situ/operando diffuse reflectance infrared Fourier transform spectroscopy-mass spectroscopy (DRIFTS-MS) coupled with density functional theory (DFT) calculations. Spectroscopic results show that bidentate carbonate formed from CO2 adsorption is hydrogenated to formate on Zn-O-Zr sites (asymmetric sites), where the Zn site is responsible for H2 activation and the Zr site is beneficial for the stabilization of reaction intermediates. The asymmetric Zn-O-Zr sites with adjacent and inequivalent features on the ZnZrOx catalyst promote not only formate formation but also its transformation. Both theoretical and experimental results demonstrate that the origin of the excellent performance of the ZnZrOx catalyst for methanol formation is associated with the H2 heterolytic cleavage promoted by the asymmetric Zn and Zr sites.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Año:
2023
Tipo del documento:
Article
País de afiliación:
China
Pais de publicación:
Estados Unidos