NbOx-Based Catalysts for the Activation of C-O and C-C Bonds in the Valorization of Waste Carbon Resources.

Escalating energy demand, the depletion of fossil fuels, and abnormal climate change are recognized as the key challenges in the 21st century. The valorization of biomass and plastic, representing the most abundant natural and man-made polymers, respectively, as alternatives to fossil fuel is one of the promising solutions to creating a carbon-neutral, waste-free society. Catalysis is an essential tool for manipulating energy transformations via bond-breaking and bond-forming principles. To producing chemicals and fuels via biomass valorization and plastic upcycling, the cleavage of C-O and C-C bonds is the major catalytic route, given that the two are mainly constructed by various interunit C-O and C-C linkages. In this work, a consensus concerning the catalytic mechanism is reached: the activities for the cleavage of C-O and C-C bonds highly depend on the catalyst ability to activate the C-O and C-C bonds. Among the catalysts reported, NbOx-based catalysts show a unique, superstrong ability to activate C-O and C-C bonds. While research on biomass valorization over NbOx-based catalysts maintains its momentum, plastic upcycling driven by an efficient NbOx-based catalyst capable of activating C-O and C-C bonds is quickly catching up. Therefore, deepening the understanding of NbOx-based catalysts for the activation of C-O and C-C bonds is of importance to further drive biomass valorization and plastic upcycling, even in many other related areas. Herein, we present progress on the activation of C-O and C-C bonds in waste carbon resources, with an emphasis on our own work in using NbOx-based catalysts. First, we introduce NbOx-based catalysts for the activation of C-O and C-C bonds in biomass with a special focus on explaining how NbOx-based catalysts activate C-O and C-C bonds and why NbOx-based catalysts can activate C-O and C-C bonds so efficiently. Then, unified descriptors to embody the abilities to extract O from oxygenated compounds and an adsorbed benzene ring, namely "oxygen affinity" and "benzene ring affinity", were defined to standardize C-O and Carom-Caliph activation chemistry. Furthermore, we highlight the emerging opportunities of NbOx-based catalysts for plastic upcycling by learning the wisdom accumulated from the activation of C-O and C-C bonds in biomass. Finally, our own insights into future recommendations in this promising field are provided.

A unified view on catalytic conversion of biomass and waste plastics.

Originating from the desire to improve sustainability, producing fuels and chemicals from the conversion of biomass and waste plastic has become an important research topic in the twenty-first century. Although biomass is natural and plastic synthetic, the chemical nature of the two are not as distinct as they first appear. They share substantial structural similarities in terms of their polymeric nature and the types of bonds linking their monomeric units, resulting in close relationships between the two materials and their conversions. Previously, their transformations were mostly studied and reviewed separately in the literature. Here, we summarize the catalytic conversion of biomass and waste plastics, with a focus on bond activation chemistry and catalyst design. By tracking the historical and more recent developments, it becomes clear that biomass and plastic have not only evolved their unique conversion pathways but have also started to cross paths with each other, with each influencing the landscape of the other. As a result, this Review on the catalytic conversion of biomass and waste plastic in a unified angle offers improved insights into existing technologies, and more importantly, may enable new opportunities for future advances.