Hydrogenation Pathways of Vapor Phase and Aqueous Solutions of Phloroglucinol on Pt

Biomass has potential as a renewable and sustainable source for several major basic feedstocks for the chemical industry.  Computational research has focused on the reaction mechanisms of key biomass reactions in vacuum through semi-empirical and Density Functional Theory (DFT).  However, computational models must also account for the role of solvent [1,2], since biomass is frequently converted to valuable products in the aqueous phase [3] .  Research has also shown that the water/metal interface is unique and plays a critical role in aqueous phase heterogeneous catalysis [4].  Hence, it is crucial to understand the effect of water on catalytic reaction mechanisms.  In our work, we present computational studies of adsorption and sequential hydrogenation of phloroglucinol on Pt(111) surfaces, since phloroglucinol can be obtained from enzymatic processing of biomass.  An explicit solvent model is used to mimic experimentally realistic phloroglucinol solutions.  We map out potential reaction pathways for conversion of phloroglucinol into valuable chemical feedstocks such as resorcinol, phenol, benzene, 1,3-cyclohexandiol, etc. 

[1]  Assary, R.S., Redfern, P.C., Hammond, J.R. Greeley, J., Curtiss, L.A. ”Computational studies of the thermochemistry for conversion of glucose to levulinic acid,” The Journal of Physical Chemistry, B. 2010, 114(27), 9002-9009.

[2] Schravendijk, P., Vegt, N. van der Delle Site, L., Kremer, K. “Dual-scale modeling of benzene adsorption onto Ni(111) and Au(111) surfaces in explicit water.” Chemphyschem: A European Journal of Chemical Physics and Physical Chemistry, 2005, 6(9), 1866-71.

[3] Moliner M, Y Roman-Leshkov, and ME Davis. 2010. “Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water.” Proceedings of the National Academy of Sciences 107:6164. DOI:10.1073/pnas.1002358107.

[3] Zope, B.N., Hibbitts, D.D., Neurock, M., Davis, R.J., “Reactivity of the gold/water interface during selective oxidation catalysis.” Science 2010, 330(6000), 74-78.