Photoreduction Mechanism of CO2 to CO Catalyzed by a Rhenium(I)-Polyoxometalate Hybrid Compound

Chenggang Ci, Jorge J. Carbó, Ronny Neumann, Coen De Graaf, Josep M. Poblet

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The photoreduction mechanism of carbon dioxide to carbon monoxide by the Re-organic hybrid polyoxometalates (POMs) {NaH[PW12O40]3-ReIL(CO)3DMA}na (L = 15-crown-5 phenanthroline, DMA = N,N-dimethylacetamide) has been investigated by means of DFT and TD-DFT calculations. The reaction mechanism can be divided into several steps, including (i) photoexcitation and charge transfer, (ii) DMA release, (iii) CO2 addition, (iv) protonation, and (v) CO release and regeneration of the catalyst. The charge transfer (CT) states, POM to Re complex, are efficiently induced by metal-centered (MC) excitations occurring on the reduced POM. Once one electron is transferred to the organometallic unit from the excited POM, the Re is able to bind and activate the CO2 substrate. Subsequent steps that involve protonation of CO2 and CO release are favorable thermodynamically and are induced by a second electron transfer from the POM to the Re complex. In this reaction, the POM acts as photosensitizer, electron reservoir, and electron donor.

Original languageEnglish
Pages (from-to)6422-6428
Number of pages7
JournalACS Catalysis
Volume6
Issue number10
DOIs
Publication statusPublished - Oct 7 2016

Fingerprint

Rhenium
Carbon Monoxide
Electrons
Protonation
Dynamic mechanical analysis
Discrete Fourier transforms
Charge transfer
Photosensitizing Agents
Photosensitizers
Phenanthrolines
Photoexcitation
Organometallics
Carbon Dioxide
Carbon monoxide
Carbon dioxide
Metals
Catalysts
polyoxometalate I
Substrates

Keywords

  • DFT
  • mechanism
  • photoreduction
  • polyoxometalate-hybrid anion
  • Re compound

ASJC Scopus subject areas

  • Catalysis

Cite this

Photoreduction Mechanism of CO2 to CO Catalyzed by a Rhenium(I)-Polyoxometalate Hybrid Compound. / Ci, Chenggang; Carbó, Jorge J.; Neumann, Ronny; Graaf, Coen De; Poblet, Josep M.

In: ACS Catalysis, Vol. 6, No. 10, 07.10.2016, p. 6422-6428.

Research output: Contribution to journalArticle

Ci, Chenggang ; Carbó, Jorge J. ; Neumann, Ronny ; Graaf, Coen De ; Poblet, Josep M. / Photoreduction Mechanism of CO2 to CO Catalyzed by a Rhenium(I)-Polyoxometalate Hybrid Compound. In: ACS Catalysis. 2016 ; Vol. 6, No. 10. pp. 6422-6428.
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