The continuous increase in manufacturing coupled with the difficulty of recycling of plastic products has generated huge amounts of waste plastics. Most of the existing chemical recycling and upcycling methods suffer from harsh conditions and poor product selectivity. Here we demonstrate a photocatalytic method to oxidize polystyrene to aromatic oxygenates under visible light irradiation using heterogeneous graphitic carbon nitride catalysts. Benzoic acid, acetophenone, and benzaldehyde are the dominant products in the liquid phase when the conversion of polystyrene reaches >90% at 150 °C. For the transformation of 0.5 g polystyrene plastic waste, 0.36 g of the aromatic oxygenates is obtained. The reaction mechanism is also investigated with various characterization methods and procedes via polystyrene activation to form hydroxyl and carbonyl groups over its backbone via C–H bond oxidation which is followed by oxidative bond breakage via C–C activation and further oxidation processes to aromatic oxygenates.

The construction of C–N bonds by the direct incorporation of dinitrogen (N2) instead of ammonia (NH3) into active species is particularly desirable but has been rarely reported. Herein, a ditantalum carbide cluster anion (Ta2C4 –) capable of cleaving the NN bond and constructing a C–N bond under mild conditions has been identified using mass spectrometry, photoelectron imaging spectroscopy, and quantum-chemical calculations. The photoelectron spectrum of Ta2C4N2 – is remarkably different from that of Ta2C4 – and matches the simulated spectrum of the Ta2C4N2 – species with an end-on-bonded CN unit. The formation of the C–N bond has also been supported by the CN– fragment observed in the collision-induced dissociation of Ta2C4N2 –. The exceptional reactivity of Ta2C4 – is ascribed to the low-valent metal center serving as an electron reservoir. This study provides a non-NH3 route to construct C–N bonds by incorporating N2 into carbide compounds to produce nitrogenous species.

Two novel small molecule acceptors (DTNIC6 and DTNIC8) based on a ladder-type dithienonaphthalene (DTN) building block with linear (hexyl) or branched (2-ethylhexyl) alkyl substituents are designed and synthesized. Both acceptors exhibit strong and broad absorption in the range from 500 to 720 nm as well as appropriate highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels. Replacing the linear hexyl chains with the branched 2-ethylhexyl chains has a large impact on the film morphology of photoactive layers. In the blend film based on DTNIC8 bearing the branched alkyl chains, morphology with well-defined phase separation was observed. This optimal phase morphology yields efficient exciton dissociation, reduced bimolecular recombination, and enhanced and balanced charge carrier mobilities. Benefited from these factors, organic solar cells (OSCs) based on PBDB-T:DTNIC8 deliver a highest power conversion efficiency (PCE) of 9.03% with a high fill factor (FF) of 72.84%. This unprecedented high FF of 72.84% is one of the highest FF values reported for nonfullerene OSCs. Our work not only affords a promising electron acceptor for nonfullerene solar cells but also provides a side-chain engineering strategy toward high performance OSCs.