Finding Furfural Hydrogenation Catalysts via Predictive Modelling

Abstract

We combine multicomponent reactions, catalytic performance studies and predictive modelling to find transfer hydrogenation catalysts. An initial set of 18 ruthenium-carbene complexes were synthesized and screened in the transfer hydrogenation of furfural to furfurol with isopropyl alcohol complexes gave varied yields, from 62% up to >99.9%, with no obvious structure/activity correlations. Control experiments proved that the carbene ligand remains coordinated to the ruthenium centre throughout the reaction. Deuterium-labelling studies showed a secondary isotope effect (kH:kD=1.5). Further mechanistic studies showed that this transfer hydrogenation follows the so-called monohydride pathway. Using these data, we built a predictive model for 13 of the catalysts, based on 2D and 3D molecular descriptors. We tested and validated the model using the remaining five catalysts (cross-validation, R2=0.913). Then, with this model, the conversion and selectivity were predicted for four completely new ruthenium-carbene complexes. These four catalysts were then synthesized and tested. The results were within 3% of the model’s predictions, demonstrating the validity and value of predictive modelling in catalyst optimization.

Designing bifunctional alkene isomerization catalysts using predictive modelling

“…9 The descriptors were ordered based on their contribution to the FOMs using the variable importance (VIP) technique. 40,41 For each FOM, we then chose those two descriptors with the highest contribution coefficients, giving a total of six important descriptors. Subsequently, we used principal component analysis (PCA) and partial least squares (PLS) regression, for building a correlation model between the descriptors and the figures of merit.…”

Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

“…Thus there is a current need for the development of soluble catalysts for FFR hydrogenation or hydrogenolysis in order to gain a better understanding of the reaction mechanism(s) and the origin of by‐products, as well as to ultimately obtain catalysts that display high activity and product selectivity. In this context, homogeneous ruthenium‐based catalysts, such as ruthenium–carbene complexes and RuCl 2 (PPh 3 ) 3 , have recently been reported to be active for FFR hydrogenation.…”

Selective Hydrogenation of the Carbonyls in Furfural and 5-Hydroxymethylfurfural Catalyzed by PtNi Alloy Supported on SBA-15 in Aqueous Solution Under Mild Conditions

“…These products and byproducts oligomers were detected by ESI-MS ( Supplementary Figure S4 ). As reported in the literature, some oligomers such as furoin ( Strassberger et al, 2010 ), 2-hydroxymethyl-5(5-furfuryl)furan, and difurfuryl ether ( Kim et al, 2011 ) could be obtained during the reaction. The active sites were not enough to convert the excess substrates under high substrate concentration, so the conversion of FF/HMF to FFA/DHMF decreased and more oligomers have been obtained leading to poor molecular carbon balance.…”