Gradient Alloyed Quantum Dots for Photocatalytic Lignin Valorization via Proton Coupled Electron Transfer

In the field of photocatalytic lignin valorization, simultaneously fulfilling the requirements of broad light harvesting and strong redox ability has been a key challenge for single binary quantum dot (QD) photocatalyst systems. In order to address the problem, gradient alloyed QDs with funnel-shaped energy structures have been developed. The gradient energy level increases the photon absorption range, while the periphery energy bands at the funnel edge are sufficiently wide to preserve effective redox capacity. In this work, the gradient alloyed QD photocatalyst along with proton donors have been employed in enhancing the efficiency and selectivity of β-O-4 bond cleavage in lignin, realizing yields of target aromatic products phenol and acetophenone to increase up to 70% and 65%, respectively. The mechanism of conversion from the ketone intermediate to target products and how to choose suitable proton donors have been systematically investigated. We propose a proton-coupled electron transfer (PCET) photocatalytic strategy through producing a C α radical from ketone with the help of acid possessing appropriate bond dissociation free energy (BDFE) and strong electronic transmission facilitating ability. The knowledge acquired in this work is useful for designing photocatalysts and proton donors that can effectively cleave bonds in lignin via the PCET mechanism.