Project

Back to overview

In silico modelling of the proton and CO2 reduction by molecular catalysts at soft interfaces

Applicant Kumanova Yordanova Tanya
Number 134151
Funding scheme Marie Heim-Voegtlin grants
Research institution Institut des sciences et ingénierie chimiques EPFL - SB - ISIC
Institution of higher education EPF Lausanne - EPFL
Main discipline Physical Chemistry
Start/End 01.02.2011 - 31.01.2013
Approved amount 211'300.00
Show all

Keywords (6)

in silico modelling; aqueous proton reduction; CO2 reduction; amphiphilic molecular catalysts; soft interfaces; reaction mechanisms

Lay Summary (English)

Lead
Lay summary
The present research proposal aims at providing a contribution to some of the most important scientific challenges of our modern society: (i) development of the renewable and sustainable source for energy as an alternative to fossil fuels and (ii) reduction of the CO2 emission in the atmosphere. Our objective is the in silico modelling of novel class of "chemical fuel cells" and investigating the routes toward the reduction of aqueous protons to H2 as well as the CO2 reduction. Of particular interest are amphiphilic molecular catalysts in the presence of organic electron donors, which are capable of performing interfacial reactions, e.g. catalysts adsorbed directly at the liquid-liquid interfaces.
With the available experimental knowledge in hands, our aim is to provide understanding and rationalization of the data, and ultimately, based on the computed structure and properties propose more efficient catalysts for these important reduction reactions. Modelling studies that address the electronic structure of active catalysts and their mechanistic pathways will be performed in order to understand how the proton and CO2 reduction take place at soft interfaces. Additionally, they will help to define the limits of applicability of the different theoretical techniques to issues of energy and electronic structure. The computational studies aimed in this proposal are by no means very challenging. Firstly, because of the high molecular complexity from a mechanistic perspective, since the reductions of protons and CO2 involve different concomitant proton and electron charge transfer reactions that are coupled as they are in bioenergetics or in certain cases, they are even concerted, i.e. occurring simultaneously. This also implies that complex potential energy surfaces have to be explored. Secondly, a proper description of electronic wavefunctions is required in order to treat in a correct way the electron correlation effects, charge transfer processes and the weak interactions. Finally, the reactions need to be modelled at the liquid-liquid interface to allow more reliable and adequate comparison with the experimental data.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Biphasic water splitting by osmocene
Ge Peiyu, Todorova Tanya Kumanova, Patir Imren Hatay, Olaya Astrid J., Vrubel Heron, Mendez Manuel, Hu Xile, Cominboeuf Clémence, Girault Hubert H. (2012), Biphasic water splitting by osmocene, in Proceedings of the National Academy of Sciences, 109(29), 11558-11563.
A multistep single-crystal-to-single-crystal bromodiacetylene dimerization
Hoheisel Tobias N., Schrettl Stephen, Marty Roman, Todorova Tanya Kumanova, Corminboeuf Clemence, Sienkiewicz Andrzej, Scopelliti Rosario, Schweizer Bernd, Frauenrath Holger, A multistep single-crystal-to-single-crystal bromodiacetylene dimerization, in Nature Chemistry.

Collaboration

Group / person Country
Types of collaboration
EPFL Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
SCS Fall Meeting 2012 13.09.2012 Zuerich, Switzerland
SCS Fall Meeting 2011 09.09.2011 Lausanne, Switzerland
Solving the Schrödinger Equation - From Electronic Structure to Quantum Dynamics (CUSO Summer School) 21.08.2011 Villars, Switzerland


Abstract

The present research proposal aims at providing a contribution to some of the most important scientific challenges of our modern society: (i) development of the renewable and sustainable source for energy as an alternative to fossil fuels and (ii) reduction of the CO2 emission in the atmosphere. Our objective is the in silico modelling of novel class of "chemical fuel cells" and investigating the routes toward the reduction of aqueous protons to H2 as well as the CO2 reduction. Of particular interest are amphiphilic molecular catalysts in the presence of organic electron donors, which are capable of performing interfacial reactions, e.g. catalysts adsorbed directly at the liquid-liquid interfaces. Modelling studies that address the electronic structure of active catalysts and their mechanistic pathways will be performed in order to understand how the proton and CO2 reduction take place at soft interfaces.
-