1. Mining the Carbon Intermediates in Plastic Waste Upcycling for Constructing C-S Bond.
- Author
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Kang, Hongxing, Kang, Hongxing, He, Dong, Turchiano, Christopher, Yan, Xingxu, Chai, Jingtong, Weed, Melanie, Elliott, Gregory, Onofrei, David, Pan, Xiaoqing, Xiao, Xiangheng, Gu, Jing, Kang, Hongxing, Kang, Hongxing, He, Dong, Turchiano, Christopher, Yan, Xingxu, Chai, Jingtong, Weed, Melanie, Elliott, Gregory, Onofrei, David, Pan, Xiaoqing, Xiao, Xiangheng, and Gu, Jing
- Abstract
Postconsumer plastics are generally perceived as valueless with only a small portion of plastic waste being closed-loop recycled into similar products while most of them are discarded in landfills. Depositing plastic waste in landfills not only harms the environment but also signifies a substantial economic loss. Alternatively, constructing value-added chemical feedstocks via mining the waste-derived intermediate species as a carbon (C) source under mild electrochemical conditions is a sustainable strategy to realize the circular economy. This proof-of-concept work provides an attractive turning trash to treasure strategy by integrating electrocatalytic polyethylene terephthalate (PET) plastic upcycling with a chemical C-S coupling reaction to synthesize organosulfur compounds, hydroxymethanesulfonate (HMS). HMS can be produced efficiently (Faradaic efficiency, FE of ∼70%) via deliberately capturing electrophilic intermediates generated in the PET monomer (ethylene glycol, EG) upcycling process, followed by coupling them with nucleophilic sulfur (S) species (i.e., SO32- and HSO3-). Unlike many previous studies conducted under alkaline conditions, PET upcycling was performed over an amorphous MnO2 catalyst under near-neutral conditions, allowing for the stabilization of electrophilic intermediates. The compatibility of this strategy was further investigated by employing biomass-derived compounds as substrates. Moreover, comparable HMS yields can be achieved with real-world PET plastics, showing its enormous potential in practical application. Lastly, Density function theory (DFT) calculation reveals that the C-C cleavage step of EG is the rate-determining step (RDS), and amorphous MnO2 significantly decreases the energy barriers for both RDS and C-S coupling when compared to the crystalline counterpart.
- Published
- 2024