Modelling electrooxidation of glycerol and methanol on close-packed transition metal surfaces
Doctoral thesis, 2020
The primary focus of this thesis is to study the reaction thermodynamics of glycerol electrooxidation on Au(111) and other close-packed late transition metal surfaces. This provides routes and products that are thermodynamically favourable, information on steps that are difficult to overcome, and at what theoretical limiting potential the reaction becomes spontaneous. Using scaling relations for adsorption energies, these results can be generalised to alloys and other possible electrode materials. We use density functional theory to model the system, and to some extent experimental verification by cyclic voltammetry. Long range dispersion (van der Waals), which have been neglected in computations until recently, is investigated by assessing density van der Waals functionals. This is of particular importance for an inert metal such as gold. Another aspect that has commonly been ignored is solvent effects, which we study for the model system of methanol electrooxidation on Au(111). This includes an implicit model - a continuous dielectric -and an explicit model of water molecules.
implicit solvation
gold
Au(111)
transition metals
biodiesel
electrochemistry
glycerol
DFT
van der Waals
methanol
scaling relations
Author
Mikael Valter
Chalmers, Physics, Chemical Physics
Geometry and Electronic Properties of Glycerol Adsorbed on Bare and Transition-Metal Surface-Alloyed Au(111): A Density Functional Theory Study
Journal of Physical Chemistry C,;Vol. 120(2016)p. 1749-1757
Journal article
Electrooxidation of Glycerol on Gold in Acidic Medium: A Combined Experimental and DFT Study
Journal of Physical Chemistry C,;Vol. 122(2018)p. 10489-10494
Journal article
Partial Electrooxidation of Glycerol on Close-Packed Transition Metal Surfaces: Insights from First-Principles Calculations
Journal of Physical Chemistry C,;Vol. 124(2020)p. 17907-17915
Journal article
Selectivity of the First Two Glycerol Dehydrogenation Steps Determined Using Scaling Relationships
ACS Catalysis,;Vol. 11(2021)p. 3487-3497
Journal article
Solvent Effects for Methanol Electrooxidation on Gold
Journal of Physical Chemistry C,;Vol. 125(2021)p. 1355-1360
Journal article
Vi fokuserar i detta arbete på den mikroskopiska processen på elektrodens yta, där glycerol fastnar och omvandlas med hjälp av elektrisk spänning. Det är viktigt att förstå hur hårt möjliga mellansteg och produkter binder till ytan, eftersom det avgör vilken väg reaktionen kommer att gå. Ett bra elektrodmaterial styr reaktionen mot de önskvärda produkterna. Syftet med detta arbete är att bygga modeller för att söka efter sådana material.
Improved Water Quality made simple by Self-cleaning Membranes
Formas (2014-1478), 2015-01-01 -- 2017-12-31.
Vågfunktionsberäkningar relevanta för hetrogen katalys med hjälp av inbäddningspotentialer
Swedish Research Council (VR) (2015-03723), 2016-01-01 -- 2019-12-31.
Areas of Advance
Transport
Energy
Materials Science
Subject Categories
Physical Chemistry
Atom and Molecular Physics and Optics
Theoretical Chemistry
Condensed Matter Physics
Roots
Basic sciences
Infrastructure
C3SE (Chalmers Centre for Computational Science and Engineering)
ISBN
978-91-7905-320-8
Doktorsavhandlingar vid Chalmers tekniska högskola. Ny serie: 4787
Publisher
Chalmers
Nexus, Fysikgården 2B
Opponent: Prof. Manos Mavrikakis, Chemical and Biological Engineering University of Wisconsin-Madison, USA