(53e) Development of in Situ Monitoring of Biomass Reactions Via Spectroscopic Techniques

Hydroxymethylfurfural (HMF) has been a target of interest in biomass upgrading as a critical steppingstone towards useful biomass-derived products. Despite recent progress in understanding the competitive reactions leading to low HMF yields, key challenges remain elusive. Among those challenges, one stands out: unravelling solvent effects at the molecular level. The lack of a holistic methodology that allows the simultaneous determination of both solvent-solute interactions and catalyst reactivity hampers our ability for establishing structure-reactivity relationships in liquid systems. While research has come a long way to understand the role solvents such as DMSO have in the success of sugar dehydration to form HMF, there are still questions left unanswered which may lead to the identification (or even prediction) of a more processing friendly solvent while maintaining or even improving current processes.

Spectroscopy is a powerful tool which can enable to discrimination of small but key changes to understand the role solvents play in stabilizing HMF and curating sugar dehydration. In this work, we will present an integrated methodology as a novel experimental protocol that can be utilized to develop fundamental understanding in biomass processing. First, we will discuss the critical role of data preprocessing in data interpretation. It is known in chemometrics that poor choice of data preprocessing methods can negatively impact the strength of a model, but it can even affect conclusion drawn. With generalized two-dimensional correlation spectroscopy (2D-COS), we will show how the presence of water and/or acid in polar aprotic solvents can affect the self-association of solvents which may have direct effect in stabilizing biomass derived molecules. Last, we will focus on developing robust calibration models as means for in-operando analysis of complex reactions.