Determining in silico the (active) surface species on Ru supported catalysts in water
Résumé
Supported ruthenium is an important heterogeneous catalyst that
is used in many transformations involving biomass valorization. Most of these
transformations are performed in liquid water under the presence of other
gas phase species i.e. a pressure of hydrogen. It is, therefore, imperative to
investigate the surface state of the underlying Ru catalyst under varying
conditions of temperature, pressure and solvent. Using periodic-DFT aided
ab-initio thermodynamics, we have studied the surface state of the Ru
catalyst in both liquid or gas water with or without an external pressure of
hydrogen. More than 800 configurations involving adsorption of H/O/OH/H2O
species on 3 different Ru surfaces were randomly generated and were
converted into thermodynamic maps in terms of temperature and pressure of
H . The solvation effects were considered using the in-house developed
Solvhybrid package which implements a hybrid QM/MM approach and makes
use of fitted UFF parameters, point charges from DFT calculation and an
alchemical transformation based on thermodynamic integration. Our results
show that under a pressure of hydrogen the most stable phase is a
monolayer of H both with and without solvation effects. However, if little or no
hydrogen pressure is supplied, the surface tends to oxidize by O/OH species
reaching a monolayer of oxygen at temperatures above 400 K. Surprisingly,
the monolayers of H/O are more solvated compared to the intact or partially
dissociated monolayer of H O. Then, those results are compared and
contrasted with the one obtained on small supported Ru particles (Ru10) on
TiO2. These results should help in our understanding of the Ru-based
catalysts and help rationalize the increased reactivity of Ru catalysts in water
in terms of its ability to generate O/OH moieties on the surface.