(730a) Catalytic Hydrogenation of Furfural over Rumop: Probing Bimetallic and Compositional Effects on Catalyst Performance

Yolanda Bonita, Timothy P. O’Connell, and Jason C. Hicks*

Department of Chemical and Biomolecular Engineering, University of Notre Dame, 182 Fitzpatrick Hall, Notre Dame, IN 46556

The synthesis of furfuryl alcohol from furfural uses an environmentally toxic copper chromite catalyst in the process. As possible alternatives, Cu-based catalysts such as supported Cu, bimetallic Cu-Ni, Cu-Co, Cu-Fe, and Cu-Ru have been studied to replace copper chromite. However, none of these catalysts surpass the high selectivity exhibited by copper chromite for furfural hydrogenation to furfuryl alcohol.

We have recently discovered a variety of novel transition metal phosphides that are highly selective to furfuryl alcohol and active at near ambient temperature. Contrary to the literature that suggested group VIII metals are not selective to furfuryl alcohol due to the binding configuration, we have synthesized group VIII metal (i.e. Ru) phosphides that exhibit high selectivity to furfuryl alcohol, similar to that of copper chromite and higher than other Cu-based catalysts. Moreover, when comparing pseudo-first order rate constants, we see an increase of > 5 times in the site-normalized, initial rate and 99% selectivity for bimetallic RuMoP. This phenomena was also observed in our previous studies (i.e. hydrodeoxygenation reaction)[1-4], which showcases bimetallic character and potential control of the catalytic properties based on catalyst composition. Indeed, we have observed direct influence on the activity and selectivity by varying the composition of Ru_xMo_2-xP, where the measured pseudo-first order rate constant was enhanced for Ru-rich materials (x = 1.2). In this presentation, we will present a thorough examination of bimetallic RuMoP as a furfural hydrogenation catalyst through detailed characterization and kinetic experiments.

References

1. Rensel, D. J., Rouvimov S., Gin M. E., Hicks J. C. Highly selective bimetallic FeMoP catalyst for C-O bond cleavage of aryl ethers. J. Catal. Sep 2013;305:256-263.
2. Rensel, D. J., Kim J., Bonita Y., Hicks J. C. Investigating the multifunctional nature of bimetallic FeMoP catalysts using dehydration and hydrogenolysis reactions. Appl. Catal. A. Aug 25 2016;524:85-93.
3. Rensel, D. J., Kim J., Jain V., Bonita Y., Rai N., Hicks J. C. Composition-directed Fe_xMo_2-xP bimetallic catalysts for hydrodeoxygenation reactions. Catal. Sci. Technol. 2017;7:1857-1867.
4. Bonita, Y., Hicks J. C. Periodic trends from metal substitution in bimetallic Mo-based phosphides for hydrodeoxygenation and hydrogenation reactions. J. Phys. Chem. C. 2018, ASAP.