Qiu Liqi, Polo-Garzon Felipe, Daemen Luke L, Kim Min-Jae, Guo Jinghua, Sumpter Bobby G, Koehler Michael R, Steren Carlos Alberto, Wang Tao, Kearney Logan T, Saito Tomonori, Yang Zhenzhen, Dai Sheng
Department of Chemistry, Institute for Advanced Materials and Manufacturing, University of Tennessee, Knoxville, Tennessee 37996, United States.
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.
J Am Chem Soc. 2025 May 14;147(19):16207-16216. doi: 10.1021/jacs.5c01107. Epub 2025 Apr 7.
Development of facile approaches to convert plastic waste into liquid fuels under neat conditions is highly desired but challenging, particularly without noble metal catalysts and an external hydrogen source. Herein, highly efficient and selective polyethylene-to-gasoline oil (branched C-C alkanes) conversion was achieved under mild conditions (<170 °C) using commercially available AlCl-containing molten salts as reaction media and to provide catalytic sites (no extra solvents, additives, or hydrogen feeding). The high catalytic efficiency and selectivity was ensured by the abundant active Al sites with strong Lewis acidity (comparable to the Al type in acidic zeolite) and highly ionic nature of the molten salts to stabilize the carbenium intermediates. Dynamic genesis of the Al sites was elucidated via time-resolved Al K-edge soft X-ray and Al NMR, confirming the tricoordinated Al as active sites and its coordination with the as-generated alkene/aromatic intermediates. The carbenium formation and polyethylene chain variation was illustrated by inelastic neutron scattering (INS) and an isotope-labeling experiment. Theoretical simulations further demonstrated the successive hydride abstraction, β-scission, isomerization, and internal hydrogen transfer reaction pathway with AlCl as active sites. This facile catalytic system can further achieve the conversion of robust, densely assembled, and high molecular weight plastic model compounds to liquid alkane products in the diesel range.
