Activities

1st March 2021, 13:00 CET, Zoom meeting

Lecture by Pr. Marc Robert from the REACTE group at the Laboratoire d’Électrochimie Moléculaire of Université Paris Diderot, France.

Title of the lecture:
“Molecular (photo)electrochemical Reduction of CO₂ with Co and Fe Complexes.
Hybrid Catalysis, Highly Reduced Products”

Abstract:

Reduction of carbon dioxide has as main objective the production of useful organic compounds and fuels – renewable fuels – in which solar energy would be stored. Molecular catalysts can be employed to reach this goal. They may in particular provide excellent selectivity thanks to easy tuning of the electronic properties at the metal and of the ligand second and third coordination sphere. Recently it has been shown that such molecular catalysts may also be tuned for generating highly reduced products (beyond CO and formate), leading to new exciting advancements.

Hybridization of these catalysts with conductive or semi-conductive materials may lead to enhance stability and new catalytic properties, as well as inclusion of molecular catalysts in devices for applications. This approach bridges between homogeneous and heterogeneous, and it raises new fundamental questions that may further lead to breakthrough in CO₂ reduction chemistry.

Our recent results in these various areas will be discussed.

References:

1. E. Boutin, M. Robert, Trends in Chemistry, 2021, in press.
2. P. B. Pati, E. Boutin, R. Wang, S. Diring, S. Jobic, N. Barreau, F. Odobel, M. Robert, Nat. Commun. 2020, 11:3499.
3. B. Ma, G. Chen, C. Fave, L. Chen, R. Kuriki, K. Maeda, O. Ishitani, T-C. Lau, J. Bonin, M. Robert,  Am. Chem. Soc. 2020, 142, 6188-6195.
4. S. Ren, D. Joulie, D. Salvatore, K. Torbensen, M. Wang, M. Robert, C. Berlinguette, Science 2019, 365, 367-369.
5. E. Boutin, M. Wang, J. C. Lin, M. Mesnage, D. Mendoza, B. Lassalle-Kaiser, C. Hahn, T. F. Jaramillo, M. Robert, Angew. Chem. Int. Ed. 2019, 58, 16172-16176.
6. Z. Guo, C. Cometto, G. Chen, L. Chen, B. Ma, H. Fan, T. Groizard, W-L. Man, S-M. Yiu, K-C. Lau, T-C. Lau, M. Robert, Nat. Catal. 2019, 2, 801-808.

Talk by NordCO₂ PhD student Simon S. Perdersen from the Interdisciplinary Nanoscience Center at Aarhus University, Denmark.

This talk is reserved for the NordCO₂ members and is accessed via Gather.

28th April 2021, 09:00 CET

Lecture by Prof. Matthias Beller, Head of the Department of Applied Homogeneous Catalysis at the Liebniz-Institut für Katalyse (LIKAT), Germany.

Title of the lecture:
“Unifying Concepts for the Development of Catalysts for Small Molecule Activation”

28th April 2021, 10:00 CET

Presentation of the 9 research groups part of the C1 Value Programme from the Academy of Finland.

28th April 2021, 12:00 CET

Lecture by Prof. Walter Leitner, Director of the Division of Molecular Catalysis at the Max Planck Institute for Chemical Energy Conversion, Germany.

Title of the lecture:
“Power-to-X catalytic conversion of carbon dioxide and hydrogen for fuels and chemicals”

20th May 2021, 14:00 CET

Lecture by Dr. Aleix Comas-Vives from the Modelling of Heterogeneous Catalysts research group at Universitat Autònoma de Barcelona, Spain.

Title of the lecture:
“Theory-Aided Comprehension of CO₂ Conversion on Heterogeneous Catalysts”

Abstract:

A transition using sustainable energy sources requires the replacement of fossil-based fuels by
synthetic energy vectors. The conversion of CO₂ to generate high-energy-density
(oxy)hydrocarbons catalyzed by heterogeneous catalysts is one of the most attractive routes for
this purpose since such materials are highly active in related CO₂/CO conversion reactions.
Theoretical calculations are crucial to understanding heterogeneous catalysts at the atomic
level. This talk will provide an overview of our recent works in the field in thermally promoted
CO₂/CO conversions,^1-7 highlighting the activity of 2D-Mo₂CTx (MXenes)⁶ and Cu single sites
supported on them (Cu@Mo₂CTx).⁷ Theoretical calculations reveal that Cu@Mo₂CTx enables
the simultaneous H₂ heterolytic cleavage and C-H bond formation steps. We suggest this is due
to the electronic nature of Cu single sites and the oxyphilic character of the support.⁷

References:
1. K. Larmier, W. C. Liao, S. Tada, E. Lam, R. Verel, A. Bansode, A. Urakawa, A. Comas-Vives*, C.
Copéret*, Angew. Chem. Int. Ed. 2017, 56, 2318-2323.
2. E. Lam, J. J. Corral-Pérez, K. Larmier, G. Noh, P. Wolf, A. Comas-Vives, A. Urakawa, C. Copéret*,
Angew. Chem. Int. Ed. 2019, 131, 14127-14134.
3. M. Silaghi, A. Comas-Vives,* C. Copéret, ACS Catal. 2016, 6, 4501-4505.
4. L. Foppa, M. Silaghi, K. Larmier, A. Comas-Vives*, J. Catal. 2016, 343, 196-207.
5. L. Foppa, T. Margossian, S. M. Kim, C. Müller, C. Copéret, K. Larmier,* A. Comas-Vives* J. Am.
Chem. Soc. 2017, 139, 17128-17139.
6. Kurlov, A.; Deeva, E. B.; Abdala, P. M.; Lebedev, D.; Tsoukalou, A.; Comas-Vives, A.; Fedorov, A.;
Müller, C. R., Nat. Commun. 2020, 11, 4920.
7. Zhou, H.; Chen, Z.; Díaz López, E.; Lam, E.; Tsoukalou, A.; Willinger, E.; Kuznetsov, D. A.; Mance,
D.; Kierzkowska, A.; Donat, F.; Abdala, P. M.; Comas-Vives, A.*; Copéret, C.*; Fedorov, A.*; Müller, C.
R.*, under revisions.

20th May 2021, 14:45 CET

 Talk by NordCO₂ PhD student Ebrahim Tayyebi from Prof. Skúlason’s research group at the University of Iceland, Iceland.

23rd June 2021, 14:00 CET

Lecture by NordCO₂ Associated PI and Assoc. Prof. Nina Lock from the Department of Biological and Chemical Engineering at Aarhus University, Denmark.

Title of the lecture:

“Metal-organic frameworks for electrocatalytic CO₂ reduction”

Abstract:

Metal-organic frameworks (MOFs) are materials consisting of metal ions connected via rigid organic ligands. MOFs exhibit permanent porosity and the exposed metal sites render MOFs promising candidates for catalysis. To date, a number of MOFs have been reported to be active for the electrocatalytic CO₂ reduction reaction. While MOFs resemble single site catalysts, they show high activity relative to the metal content, but the application of MOFs in electrocatalysis is often limited by their intrinsic poor electronic conductivity. Moreover, MOFs often have lower thermal and chemical stabilities in comparison with e.g. the corresponding metal oxides.
In this talk, approaches to increasing the electrical conductivity will be presented. Moreover, the consequences of the lacking chemical stability on the structure and electrocatalytic performance will be discussed.

24th September 2021, 14:00 CET

Lecture by Professor Julio Lloret-Fillol from the Institute of Chemical Research of Catalonia, Spain.

Title of the lecture:

“Well-Defined Catalysts for Reductive Transformations; From Solar Fuels to Fine Solar Chemicals”

Abstract:

One of the most appealing research areas is the mechanistic understanding of multi-electron multi-proton processes, which is a central part of activating small molecules such as CO₂ and H₂O.¹ Further understanding of how these mechanisms operate is essential for developing effective catalysts for sustainable energy conversion and storage.²

During the presentation, we will mainly focus on well-defined metal complexes as model systems to gain mechanistic information on CO₂ and H₂O reduction.^3-7 We will also disclose factors that could affect the catalytic activity and improve it, such as the effect of the light⁶ or inhibiting the formation of off-cycle reaction intermediates.⁷

References:

1.  M. D. Kärkäs, O. Verho, E. V. Johnston, B. Åkermark Chem. Rev. 2014, 114, 11863.
2. A. Dutta, A. M. Appel and W. J. Shaw, Nat Rev Chem 2018, 2, 244.
3. Franco, F.; Fernandez, S.; Lloret-Fillol, J. Curr. Opin. electrochemistry 2019, 15, 109
4. F. Franco, M.F. Pinto, B. Royo, J. Lloret-Fillol Angew. Chem. Int. Ed. 2018, 57, 4603
5. a) A. Call, Z. Codolà, F. Acuña-Parés, J. Lloret-Fillol, Chem. Eur. J. 2014, 20, 6171; b) A. Call, F. Franco, N. Kandoth, S. Fernández, M. González-Béjar, J. Pérez-Prieto, J.M. Luis, J. Lloret-Fillol Chem. Sci. 2018, 9, 2609; c) A. Call, C. Casadevall, F. Acuña-Pares, A. Casitas Montero, J. Lloret Fillol, Chem. Sci. 2017, 8, 4739-4749.
6. a) Fernández, S.; Franco, F.; Casadevall, C.; Martin-Diaconescu, V.; Luis, J.M.; Lloret-Fillol, J. J. Am. Chem. Soc. 2020, 142, 120. b) Fernández, S.; Cañellas, S.; Franco, F.; Luis, J. M.; Pericàs, M. A.; Lloret-Fillol, J ChemElectroChem 2021, DOI: 10.1002/celc.202100859
7. Dubed Bandomo, G. C.; et al ACS Catal. 2021, 11, 7210

21st October 2021, 14:00 CEST

Lecture by Professor James Mayer from the Mayer Lab research group at Yale University, USA.

Title of the lecture:
Fundamental properties of iron–porphyrin (electro)catalysts for O₂ reduction, with implications for CO₂ reduction

Abstract:
The chemistry of iron-porphyrin complexes with dioxygen has long been studied, inspired by the myriad examples and functions of hemes in metallobiochemistry. Kinetic studies of iron-tetraphenylporphyrin catalysis and electrocatalysis of O₂ reduction implicate pre-equilibrium O₂ binding and rate-determining protonation of the ferric-superoxide. The steps after that are kinetically invisible but have been probed by examining H₂O₂/H₂O product ratios. Three different mechanisms for the formation of hydrogen peroxide have been identified depending on catalyst structure and reaction conditions. The catalytic turnover frequencies and overpotentials have been shown to follow predictive scaling relationships. These scaling relationships are additive, either by changing multiple aspects of the catalytic system or in the unusual case with the tetra-cationic porphyrin ligand, tetra(o–N,N,N-trimethylanilinium)porphyrin. Iron complexes of this ligand are exceptional electrocatalysts for O₂ reduction, following work from Costentin, Savéant et al, showing that they are excellent for CO₂ reduction. Studies using the four different atropisomers of this catalyst indicate that the cationic charges act primarily by enhancing ancillary anionic ligand binding, more than any specific interactions with a bound O₂ or CO₂ substrate. The rapid electrocatalysis of CO₂ reduction by this catalyst depends on a very high solution concentration of phenol, and the mechanistic implications of the complex electrochemistry will be discussed.

21st October 2021, 15:00 CEST

Student talk by Morten Tysse from the Department of Chemistry at the University of Bergen.

Title of the lecture:
“Electrocatalytic Reduction of CO₂ to CO Mediated by Metal Porphyrins: Insights from DFT”

Abstract:
Iron porphyrins are among the most active electrocatalysts for the reduction of CO₂ to CO. A more recently reported candidate, zinc bacteriochlorin, has shown comparable activity and improved stability. Why the catalytic activities are similar, despite the central metal atom and the ligand both being different, is still unclear. To gain insight into the activity-determining metal and ligand factors, a density functional theory (DFT) analysis of CO₂ reduction using all the four metal–ligand (Fe/Zn–porphyrin/bacteriochlorin) was conducted. This mechanistic comparison highlights metal and ligand properties important for CO₂ to CO reduction.