Ruthenium/TiO₂‐Catalyzed Hydrogenolysis of Polyethylene Terephthalate: Reaction Pathways Dominated by Coordination Environment

Abstract

Polyethylene terephthalate (PET) hydrogenolysis can produce benzene, toluene, and xylene (BTX), where the selectivity control is challenging. We report a reaction pathway dictated by the Ru coordination environment by examining the binding geometries of adsorbates on differently coordinated Ru centers and their evolution during PET hydrogenolysis. A BTX yield of 77 % was obtained using a Ru/TiO2 with a Ru coordination number of ca. 5.0 where edge/corner sites are dominant, while more gas and saturated products were formed for Ru/TiO2 containing primarily terrace sites. Density functional theory and isotopic labelling revealed that under‐coordinated Ru edge sites favor “upright” adsorption of aromatic adsorbates while well‐coordinated Ru sites favor “flat‐lying” adsorption, where the former mitigates ring hydrogenation and opening. This study demonstrates that reaction pathways can be directed through controlled reactant/intermediate binding via tuning of the Ru coordination environment for efficient conversion of PET to BTX.

Advances in solar-driven, electro/photoelectrochemical, and microwave-assisted upcycling of waste polyesters

“…1). [26][27][28][29] These substances are then utilized in the production of new polyesters. 30,31 This approach stands out as an eco-friendly and efficient way to manage plastic waste, contributing significantly to reducing the demand for natural resources, lowering energy consumption, and mitigating the environmental concerns of plastic pollution.…”

Selective Upcycling of Polyethylene Terephthalate towards High‐valued Oxygenated Chemical Methyl p‐Methyl Benzoate using a Cu/ZrO2 Catalyst

“…[7] Similarly, Zhang et al efficiently converted of PET to BTX (Benzene, Toluene, Xylene) with yield of 77 % by tuning the Ru coordination environment in Ru/TiO 2 catalyst. [8] Interestingly, Ma et al combined a dual-promotion effect and one-pot catalytic process that subtly converting PET wastes coupling with CO 2 to the fine chemicals dimethyl cyclohexanedicarboxylate (selectivity: 28.6 %) and PX (selectivity: 49.3 %) on CuFeCr catalysts. [9] Lately, Zhao et al also reported an effective strategy that upgrading of PET into 100 % yields of PX by using methanol as both solvent and H 2 donor over the Na modified Cu/SiO 2 catalyst.…”

“…Similarly, Zhang et al. efficiently converted of PET to BTX (Benzene, Toluene, Xylene) with yield of 77 % by tuning the Ru coordination environment in Ru/TiO 2 catalyst [8] . Interestingly, Ma et al.…”

Electrochemical Co-Production of Ammonia and Biodegradable Polymer Monomer Glycolic Acid via the Co-Electrolysis of Nitrate Wastewater and Waste Plastic

“…Among all kinds of pollutants, nitrate (NO 3 – ), as a common environmental harmful pollutant, is accumulated in industrial wastewater and groundwater, leading to serious water eutrophication. − Therefore, the treatment of nitrate pollutants is urgent for purifying water resources and promoting the restoration of nitrogen cycle. Recently, a large number of waste plastics cause white pollution and endanger human health due to the excessive dependence on plastic products in human life. , As one of the largest annual output of polyester plastics, poly­(ethylene terephthalate) (PET) plastic waste is accumulated in a large number of landfills, causing groundwater and environmental pollution. , Based on this, the degradation and recycling of PET plastic waste has been widely studied. Among various reported methods (e.g., aminolysis, hydrolysis, glycolysis, and methanolysis), PET can be hydrolyzed to terephthalic acid (TPA) and ethylene glycol (EG) monomers under alkaline conditions. − Although TPA can be separated by a simple acidification process, the value-added recovery of EG is more economical and effective by controlling oxidation compared to direct separation to obtain EG.…”

“…5,6 As one of the largest annual output of polyester plastics, poly(ethylene terephthalate) (PET) plastic waste is accumulated in a large number of landfills, causing groundwater and environmental pollution. 7,8 Based on this, the degradation and recycling of PET plastic waste has been widely studied. Among various reported methods (e.g., aminolysis, hydrolysis, glycolysis, and methanolysis), PET can be hydrolyzed to terephthalic acid (TPA) and ethylene glycol (EG) monomers under alkaline conditions.…”