Frustrated Lewis pairs (FLPs), discovered in the last few decades for homogeneous catalysts and in the last few years also for heterogeneous catalysts, are stimulating the scientific community’s interest for their potential in small-molecule activation. Nevertheless, how an FLP activates stable molecules such as CO2 is still undefined. Through a careful spectroscopic study, we here report the formation of FLPs over a highly defective CeO2 sample prepared by microwave-assisted synthesis. Carbon dioxide activation over FLP is shown to occur through a bidentate carbonate bridging the FLP and implying a Ce3+-to-CO2 charge transfer, thus enhancing its activation. Carbon dioxide reaction with methanol to form monomethylcarbonate is here employed to demonstrate active roles of FLP and, eventually, to propose a reaction mechanism clarifying the role of Ce3+ and oxygen vacancies.

CeO2 Frustrated Lewis Pairs Improving CO2 and CH3OH Conversion to Monomethylcarbonate

Grillo G.;Manzoli M.;Signorile M.;Damin A.;Crocellà V.;Cravotto G.;Bordiga S.
Last
2023-01-01

Abstract

Frustrated Lewis pairs (FLPs), discovered in the last few decades for homogeneous catalysts and in the last few years also for heterogeneous catalysts, are stimulating the scientific community’s interest for their potential in small-molecule activation. Nevertheless, how an FLP activates stable molecules such as CO2 is still undefined. Through a careful spectroscopic study, we here report the formation of FLPs over a highly defective CeO2 sample prepared by microwave-assisted synthesis. Carbon dioxide activation over FLP is shown to occur through a bidentate carbonate bridging the FLP and implying a Ce3+-to-CO2 charge transfer, thus enhancing its activation. Carbon dioxide reaction with methanol to form monomethylcarbonate is here employed to demonstrate active roles of FLP and, eventually, to propose a reaction mechanism clarifying the role of Ce3+ and oxygen vacancies.
2023
15
12
15396
15408
CeO; 2; CO; 2; activation; dimethyl carbonate; frustrated Lewis pair; monomethylcarbonate
Salusso D.; Grillo G.; Manzoli M.; Signorile M.; Zafeiratos S.; Barreau M.; Damin A.; Crocellà V.; Cravotto G.; Bordiga S.
File in questo prodotto:
File Dimensione Formato  
acsami.2c22122.pdf

Open Access dal 31/03/2024

Tipo di file: PDF EDITORIALE
Dimensione 6.14 MB
Formato Adobe PDF
6.14 MB Adobe PDF Visualizza/Apri
am2c22122_si_001.pdf

Open Access dal 31/03/2024

Tipo di file: DATASET
Dimensione 1.44 MB
Formato Adobe PDF
1.44 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1903674
Citazioni
  • ???jsp.display-item.citation.pmc??? 2
  • Scopus 12
  • ???jsp.display-item.citation.isi??? 9
social impact