Cerium coordination-dependent surface intermediates regulate activity in dimethyl carbonate synthesis from CO2 and methanol

Linyuan Tian, Zicong Tan, Quan Wang, Yin-Song Liao, Jyh-Pin Chou*, Jyh-Ming Wu, Guoliang Liu*, Yung-Kang Peng*

*Corresponding author for this work

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

32 Citations (Scopus)

Abstract

The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol is a potential green alternative to the current industrial methods using toxic chemicals. Although many CeO2-based catalysts have been explored, the key structural factor affecting their DMC activity is still unclear. Herein, single-crystalline CeO2 catalysts bearing distinct but well-defined Ce coordination structures were examined. We found that methanol is the key species being activated by surface Ce sites (cf. CO2) to produce methyl carbonate (MC) and later DMC. The reactivity of surface methoxy species towards CO2 varies considerably with its configuration determined by Ce coordination structures. The head-to-head terminal methoxy species converts CO2 to MC faster than its atilt counterparts, resulting in a higher DMC activity. The bridging methoxy species is, however, too stable to react with CO2. The established structure-activity relation here should also guide the design of CeO2-based catalysts in other reactions involving methanol activation. © 2023 Elsevier B.V.
Original languageEnglish
Article number122914
JournalApplied Catalysis B: Environmental
Volume336
Online published24 May 2023
DOIs
Publication statusPublished - 5 Nov 2023

Funding

We thank the Hong Kong Research Grants Council (CityU 21301719 and 11300020) and the Strategic Interdisciplinary Research Grant of City University of Hong Kong (Project No. 7020053). J.C. Chou acknowledges financial support from the MOST, Taiwan (MOST-109-2112-M-018-008-MY3) and National Center for High-performance Computing (NCHC) of National Applied Research Laboratories (NARLabs) in Taiwan for providing computational and storage resources.

Research Keywords

  • CeO2
  • Coordination structure
  • Dimethyl carbonate
  • Structure-activity relation
  • Surface methoxy species

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