In:
Green Chemistry, Royal Society of Chemistry (RSC), Vol. 24, No. 7 ( 2022), p. 2988-3000
Abstract:
The advanced coupled conversion technique based on the oxidative dehydrogenation (ODH) of alcohols and the reduction of CO 2 is a potential strategy to solve the current energy and environmental crisis, and is of great significance for the upgrading conversion of CO 2 to fuels. This work discloses that the Al 3+ species-doped decatungstates (Al-DTs) can efficiently catalyze the coupled conversion of various aliphatic and aromatic primary/secondary alcohols with CO 2 in MeCN under visible light illumination and very mild conditions, and the reductive efficiency of CO 2 depends on the doping levels of Al 3+ species in Al-DTs and the ODH reactivity of alcohols. After continuously illuminating for 12 h, the best, 4% Al-DT can provide 437 μmol acetophenone as the ODH product and 218 μmol CO 2 reduction products (formic acid and methanol) with 1.82 h −1 turnover frequency in the photocatalytic coupled conversion of α-phenylethanol with CO 2 . Also, a trace amount of CO is detected from the photocatalytic coupled reactions. UV-vis spectra and isotope tracing tests using heavy oxygen water (H 2 18 O) support that the doubly-reduced blue H 2 DT species generated from the photocatalytic ODH of alcohols turns into its oxygen-deficient form ([DT 2− ] v ) via an intra-molecular dehydration or lattice oxygen transfer and the latter, with the help of doped Al 3+ species, may efficiently reduce CO 2 to fuels via the multi-step proton-coupled electron transfer (PET) pathway.
Type of Medium:
Online Resource
ISSN:
1463-9262
,
1463-9270
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
detail.hit.zdb_id:
1485110-6
detail.hit.zdb_id:
2006274-6
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