Carbonyl CO bond reduction via catalytic transfer hydrogenation (CTH) is one of the essential processes for biomass conversion to valuable chemicals and fuels. Here, we investigate the CTH of furfural to furfuryl alcohol with i-propanol on UiO-66 metal–organic frameworks using density functional theory calculations and linear scaling relations. Initially, the reaction over two defect sites presented on Zr-UiO-66, namely, dehydrated and hydrated sites, have been compared. The hydrated active site is favored over that on the dehydrated active site since the activation free energy of the rate-determining reaction step occurring on the hydrated active site is lower than that occurring on the dehydrated active site (14.9 vs 17.9 kcal/mol). The catalytic effect of exchanged tetravalent metals (Hf and Ti) on Zr-UiO-66 is also considered. We found that Hf-UiO-66 (13.5 kcal/mol) provides a lower activation energy than Zr-UiO-66 (14.9 kcal/mol) and Ti-UiO-66 (19.4 kcal/mol), which corresponds to it having a higher Lewis acidity. The organic linkers of UiO-66 MOFs play a role in stabilizing all of the species on potential energy surfaces. The linear scaling relationship also reveals the significant role of the UiO-66 active site in activating the carbonyl CO of furfural, and strong relationships are observed between the activation free energy, the charge of the metal at the MOF active sites, and the complexation energies in reaction coordinates.

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