Photocatalytic production of ethylene and propionic acid from plastic waste by titania-supported atomically dispersed Pd species.

Zhang, Shuai; Xia, Bingquan; Qu, Yang; Jing, Liqiang; Jaroniec, Mietek; Ran, Jingrun; Qiao, Shi-Zhang · Sci Adv · 2023

basic_science · Level V

Where this comes from

Abstract

Current chemical recycling of bulk synthetic plastic, polyethylene (PE), operates at high temperature/pressure and yields a complex mixture of products. PE conversion under mild conditions and with good selectivity toward value-added chemicals remains a practical challenge. Here, we demonstrate an atomic engineering strategy to modify a TiO<sub>2</sub> photocatalyst with reversible Pd species for the selective conversion of PE to ethylene (C<sub>2</sub>H<sub>4</sub>) and propionic acid via dicarboxylic acid intermediates under moderate conditions. TiO<sub>2</sub>-supported atomically dispersed Pd species exhibits C<sub>2</sub>H<sub>4</sub> evolution of 531.2 μmol g<sub>cat</sub><sup>-1</sup> hour<sup>-1</sup>, 408 times that of pristine TiO<sub>2</sub>. The liquid product is a valuable chemical propanoic acid with 98.8% selectivity. Plastic conversion with a C<sub>2</sub> hydrocarbon yield of 0.9% and a propionic acid yield of 6.3% was achieved in oxidation coupled with 3 hours of photoreaction. In situ spectroscopic studies confirm a dual role of atomic Pd species: an electron acceptor to boost charge separation/transfer for efficient photoredox, and a mediator to stabilize reaction intermediates for selective decarboxylation.