Transitioning away from fossil fuels in the energy and chemical sectors is crucial to achieving a sustainable and environmentally friendly future. One promising approach in this transition is the utilization of glycerol, a byproduct of biodiesel production, as a plentiful and renewable source for producing valuable chemicals. Glycerol's valorization not only provides a sustainable alternative to fossil fuels but also adds value to biodiesel production by converting its byproduct into high-value chemicals. However, the process of converting glycerol is complex due to the intricate reaction mechanisms involved, which significantly impact the selection of products. This study delves into the chemical selectivity of glycerol when catalyzed by various metallic surfaces, focusing on the use of specific descriptors for carbon (*C, *CH2OH) and oxygen (*O, CH3O). By employing linear regression analysis, we discovered that CH2OH and CH3O are superior descriptors compared to *C and *O, respectively. This superiority is attributed to their unique interactions with adjacent groups and specific bond characteristics, which influence the reaction intermediates and overall reaction pathway.

To validate these findings, we conducted multilinear regression analyses, further supporting the effectiveness of CH2OH and CH3O as descriptors. The research progressed by utilizing scaling relationships to develop selectivity maps for glycerol dehydrogenation. These maps serve as a valuable tool in identifying potential catalyst candidates by illustrating the selectivity trends based on the relative bond strengths of carbon and oxygen descriptors on different metallic surfaces. The study's results indicate that the first dehydrogenation step of glycerol can lead to two different intermediates, each bonded through either the secondary carbon or the secondary oxygen, depending on the relative bond strengths of the descriptors. In the subsequent dehydrogenation step, up to five intermediates may form, again influenced primarily by the bond strength interactions of carbon and oxygen with the catalyst surface. These detailed selectivity maps, in combination with kinetic considerations and experimental data, offer a comprehensive guide for selecting and optimizing catalysts for efficient glycerol dehydrogenation.

In conclusion, this research provides significant insights into the valorization of glycerol, highlighting the importance of selecting appropriate descriptors for understanding and controlling the reaction mechanisms involved. The development of selectivity maps presents a practical approach to predicting and enhancing catalyst performance, paving the way for more efficient and sustainable chemical production processes from glycerol. By addressing the complexities of glycerol valorization, this study contributes to the broader goal of transitioning away from fossil fuels. The findings emphasize the potential of using renewable feedstocks and advanced catalysis to produce high-value chemicals, supporting the shift towards a more sustainable and circular economy. This research not only advances the understanding of glycerol chemistry but also offers practical solutions for developing greener technologies in the energy and chemical sectors.