Partial Electrooxidation of Glycerol on Close-Packed Transition Metal Surfaces: Insights from First-Principles Calculations
Artikel i vetenskaplig tidskrift, 2020

Glycerol is a byproduct of biodiesel production and an abundant feedstock for the synthesis of high-value chemicals. One promising approach for valorization of glycerol is electrooxidation yielding hydrogen and value-added products. However, due to the vast amount of intermediary steps and possible products, the process is not fully understood. Here, the first two deprotonations of glycerol on close-packed transition metals (Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au) are investigated using density functional theory calculations together with the computational hydrogen electrode. We find that the theoretical limiting potential for the studied reaction is close to 0 V vs the reversible hydrogen electrode, ranging from −0.12 V for ruthenium to +0.35 V for gold. Furthermore, the results show that Ru, Rh, Ir, Ag, and Au are selective toward dihydroxyacetone and its derivatives, while Pd and Pt are selective toward either dihydroxyacetone or glyceraldehyde and their derivatives, and that Cu, Co, and Ni are selective toward hydropyruvic acid. The results can be rationalized in terms of the relative bond strengths of carbon and oxygen on the metal. In addition, we find that solvent effects are generally small, the exceptions being the limiting potential on copper and the mechanism on rhodium. These results can be used to steer the selectivity toward more valuable products and thereby increase the economic yield of biodiesel production.

Författare

Mikael Valter

Chalmers, Fysik, Kemisk fysik

Egon Campos Dos Santos

Stockholms universitet

Lars GM Pettersson

Stockholms universitet

Anders Hellman

Chalmers, Fysik, Kemisk fysik

Journal of Physical Chemistry C

1932-7447 (ISSN) 1932-7455 (eISSN)

Vol. 124 33 17907-17915

Ämneskategorier

Oorganisk kemi

Fysikalisk kemi

Annan fysik

Drivkrafter

Hållbar utveckling

Styrkeområden

Nanovetenskap och nanoteknik (SO 2010-2017, EI 2018-)

Transport

Energi

Materialvetenskap

Infrastruktur

C3SE (Chalmers Centre for Computational Science and Engineering)

DOI

10.1021/acs.jpcc.0c04002

Mer information

Senast uppdaterat

2020-09-24