Publisher: American Chemical Society (ACS)

Issue: 26

License: [{"start"=>{"date-parts"=>[[2025, 6, 19]], "date-time"=>"2025-06-19T00:00:00Z", "timestamp"=>1750291200000}, "content-version"=>"vor", "delay-in-days"=>0, "URL"=>"https://creativecommons.org/licenses/by/4.0/"}]

Publication date(s): 2025/07/03 (print) 2025/06/19 (online)

Pages: 12676-12688

Volume: 39 Issue: {"issue"=>"26", "published-print"=>{"date-parts"=>[[2025, 7, 3]]}}

Journal: Energy & Fuels

Link: [{"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acs.energyfuels.5c01580", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"}, {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acs.energyfuels.5c01580", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

Upgrading biorefinery-derived waste such as glycerol to fuel-additives and high-value products is essential to further enhance the productivity, profitability, and circularity of the biorefinery concept to achieve a green and sustainable net-zero world. This study explores the catalytic conversion of glycerol into glycerol carbonate using calcium oxide–cerium oxide (CaO–CeO₂) dual-function catalytic materials. Herein, a clean and efficient approach was developed to synthesize CaO–CeO₂ materials using a green mechanochemical method and then utilize these as catalyst in sustainable and solvent-free synthesis of glycerol carbonate to enhance the circular economy of biorefineries while reducing their carbon footprint. The catalysts were comprehensively characterized using XRD, FTIR, ICP, N₂ sorption, CO₂-TPD, and SEM/EDS analyses and evaluated for their catalytic activity. Among the catalysts studied, 40 wt % CaO–CeO₂ exhibited the highest catalytic activity, achieving 95% glycerol conversion and 99% selectivity to glycerol carbonate under optimized conditions (10 wt % catalyst loading relative to glycerol, 90 °C, 60 min, and a glycerol/ DMC molar ratio of 1:3). This catalyst showed excellent reusability, maintaining high conversion over four cycles. The transesterification reaction followed irreversible second-order reaction kinetics with an activation energy of 46.9 kJ mol^–1. The synergistic interplay between the basic sites of the Ca²⁺–O^2– pair and the oxygen vacancies in the CeO₂ matrix at the CaO–CeO₂ interface work in tandem to enhance the catalytic activity for glycerol carbonate production. We have developed a highly efficient, cost-effective, and environment-friendly approach for the sustainable production of glycerol carbonate from glycerol.

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