Joby Sebastian

Biomass presents an attractive resource for a sustainable production of platform chemicals and monomers. Especially N‐containing compounds are broadly utilized as solvents, in polymer production and as fine chemicals or pharmaceutics. An important compound is N‐vinyl‐pyrrolidone used for polyvinylpyrrolidone production (PVP). Today it is produced based on fossil acetylene via Reppe chemistry and vinylation. However, it can be accessed from biomass‐derived succinic acid by reductive amination with ethanolamine and hydrodeoxygenation followed by dehydration of the ethanol group to provide the vinyl functionality. Previous studies identified selective hydrodeoxygenation of the intermediate N‐(2‐hydroxyethyl)succinimide (HESim) as crucial to achieve high selectivity and yield. At the same time, an LCA study highlighted the significant impact of selective product formation on the CO ₂ ‐footprint of this route. This study discusses bimetallic Pt/X (X = V, Cu, Ni, Co, and Mo) catalysts supported on TiO ₂ for efficient hydrodeoxygenation of HESim. Aiming for high activity and overall performance, alternative metal combinations were screened and recycling experiments conducted. Combining Pt and Mo on TiO ₂ allowed achieving 97% HESim conversion and 95% yield of the two desired products N‐(2‐hydroxyethyl)‐2‐pyrrolidone (HEP) and 4‐hydroxy‐N‐(2‐hydroxyethyl)‐butanamide (HEBA). Accordingly, Pt/Mo on TiO ₂ outperforms the previous literature best performer based on a supported Pt/Re‐catalyst.

The concept of strong metal‐support interaction (SMSI), a topic of investigation for over four decades, remains an important area of research in heterogeneous catalysis. While substantial progress has been made in understanding SMSI across various metal/support systems, its complexity continues to evolve. TiO ₂ , recognized as the first support material to exhibit SMSI, has been instrumental in advancing this understanding. However, the lack of a comprehensive guide on how various factors influence SMSI on TiO ₂ has limited the ability to systematically control these interactions. This review seeks to provide a consolidated view of the current understanding of SMSI in TiO ₂ ‐supported metal catalysts. It highlights the sensitivity of SMSI on TiO ₂ to a range of parameters, including pretreatment conditions and reaction environments. The dynamic nature of SMSI under reaction conditions is also explored, underscoring its complexity and potential for fine‐tuning catalyst performance. Additionally, practical insights into innovative chemical methods for controlling SMSI on TiO ₂ are discussed, offering strategies for modulating SMSI to meet specific catalytic requirements. By addressing these aspects, this review aims to offer a valuable guide for the rational design of metal/TiO ₂ catalysts, ultimately contributing to a more refined and controllable approach to SMSI on TiO ₂ .

Bisphenol A (BPA), a key monomer used in polymer production, poses significant health and environmental risks, necessitating the need for sustainable alternatives. This study establishes a sustainable route for BPA alternatives via the acetalization of biomass‐derived vanillin and erythritol using industrially relevant zeolite catalysts. Among various homogeneous and heterogeneous Brønsted and Lewis acid catalysts tested, heterogeneous mordenite zeolite (SiO₂/Al₂O₃ = 40) achieves the highest BPA derivative yield (90%). Kinetic studies confirm a consecutive reaction mechanism, with the hemiacetal‐to‐acetal step being the rate‐determining step. The catalyst is recyclable and maintains stable performance over five consecutive runs. Detailed structural characterizations, reactant accessibility studies, conditional experiments, and probe molecule tests reveal that a higher external surface area, Brønsted acid sites on the external surface, and greater hydrophobicity are key to the zeolite's high efficiency. These features facilitate the adsorption and desorption of large reactant and product molecules, circumventing pore‐diffusion limitations while evading byproduct water‐induced deactivation. This study not only demonstrates the use of industrial zeolites for sustainable BPA derivatives from biorenewables but also highlights critical structural and compositional parameters for optimizing catalyst design. Also, the findings provide a framework for rationalizing zeolite‐based catalysts for a broad range of biobased BPA alternatives.