open access

https://hdl.handle.net/2115/91443

Adsorption of CO2 on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

英語

Adsorption

2023-04-13

American Chemical Society

Journal of physical chemistry c

127(14)

6998-7008

Herein, we study the structural and electronic origins of molecular adsorption using experiments and density functional theory (DFT) calculations. We performed X-ray diffraction (XRD) and temperature-programmed desorption (TPD) of CO2 on amorphous zirconia (amZrO2) and crystalline (tetragonal and monoclinic) zirconia. Using molecular dynamics simulations, the bulk structures of am-ZrO2 and amzirconium(IV) hydroxide (am-Zr(OH)4) were obtained and the reproducibility of the experimental structure was confirmed by comparing the radial distribution functions. In addition, the hydroxyl density on the hydrogenated ZrO2 surfaces was found to be consistent with the experimental results. Both experiments and simulations indicate that the adsorption of CO2 on an am-ZrO2 surface is more heterogeneous and weaker than that on a crystalline zirconia surface. Because the charge environment and band structures of crystalline zirconia are approximately the same as those of am-ZrO2, the weak adsorption on the am-ZrO2 surface arises from the fewer and stronger Zr-O bonds on the surface. These findings provide molecular-level insight not only for the adsorption of CO2 but also into the molecular adsorption on ZrO2-based catalysts.

学術雑誌論文

Accepted Manuscript

This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-TJG84G2ADX76N4FB8WY7.

1932-7447