Pressing environmental issues such as the impact of Greenhouse Gas (GHG) or the depletion of natural resources have become increasingly publicized in the media. As a result, the society has become aware on a global scale about the need of sustainable development defined as development that “meets the needs of the present generation without compromising the ability of future generations to meet their own needs”. The latest United Nations Climate Change Conference was held in Cancun, Mexico in 2010. If a treaty was not signed, the agreement reached was described by the New York Times as a “major step forward”. Climate change was recognized as an urgent threat for the society and the planet and some drastic cuts in GHG emissions were deemed essential. A report supported by CEFIC (European Chemical Industry Council) in 2009 argued that if the chemical industry is part of the climate change issue it is also part of the solution.
Since CO2 is a source of carbon it could be considered as an attractive building block for chemistry given its low cost and abundance. Unfortunately, CO2 is highly stable and its low reactivity is a clear challenge to develop new chemical reactions. In particular, the chemical industry is developing solutions to capture, compress and store (CCS) CO2. It has been estimated that the potential reduction of Green House Gases (GHG) through CCS could reach 1 to 1.5 GT by 2050. . However, only 1 ‰ of the total abundance of CO2 is currently being used for chemical synthesis, which is mainly caused by its chemical inertness and the high costs of CO2 capture and storage. Currently, CO2is used in the chemical industry for the production of bulk chemicals such as urea, salicylic acid, cyclic carbonates, and polypropylene carbonate using heterogeneous catalysts. Heterogeneous catalysis is still the state-of-the-art for the large-scale transformation of CO2 but those processes are not selective enough to transform CO2 in more sophisticated molecules, such as fine chemicals or pharmaceutical agents. Furthermore, CO2 can also be utilized by reduction to CO, methane, methanol or carboxylates. However, the reduction to CO, methane and methanol are thermodynamically unfavorable and the high energy barriers can be only be overcome by implementing catalysts. In addition to carbamates and cyclic carbonates, electrochemical fixation of CO2 to afford valuable carboxylic acids has been demonstrated on alkenes [[i],[ii],[iii],[iv],[v],[vi],[vii],[viii],[ix],[x],[xi]], alkynes [[xii],[xiii],[xiv],[xv],[xvi],[xvii],[xviii]], carbonyl groups [[xix],[xx],[xxi],[xxii],[xxiii],[xxiv],[xxv],[xxvi]], halogenated ketones [[xxvii]], alkyl/aryl/acyl [2,[xxviii],[xxix],[xxx],[xxxi],[xxxii],[xxxiii],[xxxiv],[xxxv]] and allylic [[xxxvi],[xxxvii]] halides, vinyl triflates [[xxxviii],[xxxix],[xl]], amides [[xli]] and heterocyclic compounds [[xlii],[xliii]].
As mentioned above, carbon dioxide has a big potential to become a cheap feedstock in chemistry to form reduced carbon species as energy source or by forming C-C bonds to form sophisticated molecules. However, until now there is no eco-efficient process available that achieves those goals. This is due to the high stability of CO2 which makes its activation very difficult. Known catalysts do not show high selectivity or turnover rates and some even need to be destroyed during the work up of the products.
Our goal is to achieve understanding of the activation of CO2 towards C-C bond formation which could serve as monomers for advanced polymers. We develop tools and models in order to study the homogeneous, heterogeneous and electrochemical catalytic activation of carbon dioxide. Both, DFT simulations and experiments are working hand in hand. The achieved knowledge can then be used to design optimal catalysts and reaction parameters for a chosen application.
- Rotating disc electrochemical high pressure reactor capable to run at supercritical CO2
- Batch reactor, designed for feeding low pressure gas (e.g. butadiene), then adding carbon dioxide to regulate the pressure
- Sampling of gas and liquid either per syringe or at the sampler
- Later introduction of reactant solution possible
- 4 electrode positions are included: either for use of rotating disc or as parallel standard setup where the rotating disc can be changed to a stirrer
- For homogeneous catalysis: Quantum mechanical DFT studies using Gaussian combined with the XO model to investigate homogeneous catalytic activation and verify reaction pathways
- For heterogeneous catalysis: Quantum mechanical DFT studies using Gaussian with implemented electrochemistry.
- Use of correlation methods QSAR for screening catalysts
Capture & Separation:
"Modelling the HCOOH/CO2 Electrochemical Couple: When Details Are Key", S. Steinmann, C. Michel, R. Schwiedernoch, J.-S. Filhol, P. Sautet; ChemPhysChem, Article first published online: 10 JUN 2015
“Impact of Electrode Potential and Solvent on the Electroreduction of CO2: A Comparison of Theoretical Approaches”, S. Steinmann, C. Michel, R. Schwiedernoch, P. Sautet; Physical Chemistry Chemical Physics, (2015), 17, 13949-13963.
“Formation of acrylates from ethylene and CO2 on Ni complexes: A mechanistic viewpoint from a hybrid DFT approach”, W. Guo, C. Michel, R. Schwiedernoch, R. Wischert, X. Xu, P. Sautet; Organometallics, (2014), 33 (22), pp 6369–6380.
- "Porous Inorganic Membranes for CO2 capture: present and prospects", M. Pera-Titus, Chem. Rev, (2014), 114 (2), 1413–1492.
- "Nanocomposite MFI-Alumina Hollow Fiber Membranes: Influence of NOx and Propane on CO2/N2 Separation Properties", C-H. Nicolas, M. Pera-Titus; Ind. Eng. Chem. Res. 51 (2012),10451-10461.
- [i] M.A. Chowdhury, H. Senboku, M. Tokuda, Electrochemical carboxylation of bicyclo[n.1.0]alkylidene derivatives, Tetrahedron 60, 2004, 475-481.
- [ii] D.A. Tysee, J.H. Wagenknecht, M.M. Baiter, and J.L. Chruma, Some cathodic organic syntheses involving carbon dioxide, Tetrahedron Lett. 47, 1972, 4809-4812.
- [iii] S. Gambino, G. Filardo, G. Silvestri, Electrochemical carboxylation of organic substrates. Synthesis of carboxylic derivatives of acenaphthylene, J. Applied Electrochem. 12, 1982, 549-555.
- [iv] G. Filardo, S. Gambino, G. Silvestri, A. Gennaro, E. Vianello, Electrocarboxylation of styrene through homogeneous redox catalysis, J. Electroanal. Chem. 177, 1984, 303-309.
- [v] S. Derien, J-C. Clinet, E. Dunach, J. Perichon, Electrochemical incorporation of carbon dioxide into alkenes by nickel complexes, Tetrahedron Lett. 48, 1992, 5235-5248.
- [vi] D.A. Tyssee, M.M. Balzer, Electrocarboxylation. I. Mono- and decarboxylation of activated olefins, J. Org. Chem. 39, 1974, 2819-2823.
- [vii] S.W. Wawzoteck, A. Gundersen, Polarographic studies in acetonitrile and dimethylformamide. IX. Behavior of a,b-unsaturated carbonyl compounds, J. Electrochem. Soc. 111, 1964, 324-328.
- [viii] S.W. Wawzoteck, L.W. Blaha, R. Berkey, M.E. Runner, Polarographic studies in acetonitrile and dimethylformamide. II. Behavior of aromatic olefins and hydrocarbons, J. Electrochem. Soc. 102, 1955, 235-242.
- [ix] J. Bringmann, E. Dinjus, Electrochemical synthesis of carboxylic acids from alkenes using various nickel-organic mediators: CO2 as C1-synthon, Applied Organometal. Chem. 15, 2001, 135-140.
- [x] D. Ballivet-Tkatchenko, J-C. Folest, J. Tanji, Applied Organometal. Chem. 12, 2000, 847-849.
- [xi] G-Q. Yuan, H-F. Jiang, C. Lin, S.J. Liao, Efficient electrochemical synthesis of 2-arylsuccinic acids from CO2 and aryl-substituted alkenes with nickel as a cathode, Electrochim. Acta 53, 2008, 2170-2176.
- [xii] E. Dunach, S. Derien, J. Perichon, Nickel-catalyzed reductive electrocarboxylation of disubstituted alkynes, J. Organometal. Chem. 364, 1989, C33-C36.
- [xiii] G-C. Yuan, H-F. Jiang, C. Lin, Efficient electrochemical dicarxylations of arylacetylenes with carbon dioxide using nickel as a cathode, Tetrahedron 64, 2008, 5866-5872.
- [xiv] K. Shimizu, M. Takimoto, Y. Sato, M. Mori, Nickel-catalyzed regioselective synthesis of tetrasubstituted alkene using alkylative carboxylation of disubstituted alkyne, Org. Lett. 7, 2005, 195-197.
- [xv] D. Walther, H. Schönberg, E. Dinjus, Aktivierung von Kohlendioxid an Übergangsmetallzentren: Selektive Cooligomerisation mit Hexin(-3) durd das Katalysorsystem Acetonitril/Trialkylphosphan/Nickel(0) und Struktur eines Nikel(0)-Komplexes mide side-on gebundenem Acetonitril, J. Organometal. Chem. 334, 1987, 377-388.
- [xvi] E. Dunach, J. Perichon, Electrochemical carboxylation of terminal alkynes catalysed by nickel complexes: unusual regioselectivity, J. Organometal. Chem. 352, 1988, 239-246.
- [xvii] S. Derien, E. Dunach, J. Perichon, Electrochemical carboxylation of terminal alkynes catalysed by nickel complexes: unusual regioselectivity, From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis, J. Organometal. Chem. 113, 1991, 8447-8454.
- [xviii] F. Koster, E. Dinjus, E. Dunach, Electrochemical selective incorporation of CO2 into terminal alkynes and diynes, Eur. J. Org. Chem., 2001, 2507-2511.
- [xix] O. Scialdone, A. Galia, C. La Rocca, G. Filardo, Influence of the nature of the substrate and of operative parameters in the electrocarboxylation of halogenated acetophenones and benzophenones, Electrochim. Acta 50, 2005, 3231-3242.
- [xx] G. Silvestri, S. Gambino, G. Filardo, Electrochemical carboxylation of aldehydes and ketones with sacrificial aluminium electrodes, Tetrahedron Lett. 27, 1986, 3429-3430.
- [xxi] O. Scialdone, C. Amatore, A. Galia, G. Filardo, CO2 as a C1-organic building block: Electrocarboxylation of aromatic ketones. A quantitative study of the effect of the concentration of substrate and of carbon dioxide on the selectivity of the process, J. Electroanal. Chem. 592, 2006, 163-174.
- [xxii] O. Scialdone, A. Galia, A.A. Isse, A. Gennaro, M.A. Sabatino, R. Leone, G. Filardo, Electrocarboxylation of aromatic ketones: Influence of operative parameters on the competition between ketyl and ring carboxylation, J. Electroanal. Chem. 609, 2007, 8-16.
- [xxiii] O. Scialdone, M.A. Sabatino, C. Belfiore, A. Galia, M.P. Paternostro, G. Filardo, An unexpected ring carboxylation in the electrocarboxylation of aromatic ketones, Electrochem. Acta 51, 2006, 3500-3505.
- [xxiv] R. Engels, C.J. Smith, W.J.M. van Tilborg, Reactions at the counter electrode in electroreductions under aprotic conditions in one-compartment cells, Angew. Chem. Int. Ed. 22, 1983, 492-493.
- [xxv] A.S.C. Chan, T.T. Huang, J.H. Wagenknecht, R.E. Miller, A novel synthesis of 2-aryllactic acids via electrocarboxylation of methyl aryl ketones, J. Org. Chem. 60, 1995, 742-744.
- [xxvi] A.K. Datta, P.A. Marron, C.J.H. King, J.H. Wagenknecht, Process development for electrocarboxylation of 2-acetyl-6-methoxynaphthalene, J. Applied Electrochem. 28, 1998, 569-577.
- [xxvii] A.A. Isse, A. Galia, C. Belfiore, G. Silvestri, A. Gennaro, Electrochemical reduction and carboxylation of halobenzophenones, J. Electroanal. Chem. 526, 2002, 41-52.
- [xxviii] J. Damodar, S.R.K. Mohan, S.R.J. Reddy, Synthesis of 2-arylpropionic acids by electrocarboxylation of benzylchlorides catalysed by PdCl2(PPh3)2, Electrochem. Commun. 3, 2001, 762-766.
- [xxix] V.G. Koshechko, V.E. Titov, V.A. Lopushanskaya, Electrochemical carboxylation of benzoyl bromide as effective phenylglyoxylic acid synthesis route, Electrochem. Commun. 4, 2002, 655-658.
- [xxx] J.H. Wagenknech, Electroreduction of alkyl halides in the presence of CO2, Electroanal. Chem. Interf. Electrochem. 52, 1974, 489-492.
- [xxxi] A.A. Isse, A. de Giusti, A. Gennaro, One- versus two-electron reaction pathways in the electrocatalytic reduction of benzyl bromide at silver cathodes, Tetrahedron Lett. 47, 2006, 7735-7739.
- [xxxii] O. Sock, M. Troupel, J. Perichon, Electrosynthesis of carboxylic acids from organic halides and carbon dioxide, Tetrahedron Lett. 26, 1985, 1509-1512.
- [xxxiii] J.F. Fauverque, Y. de Zelicourt, C. Amatore, A. Jutand, Nickel-catalysed electrosynthesis of anti-inflammatory agents. III. A new electrolyser for organic solvents; oxidation of metal powder as an alternative to sacrificial anodes, J. Applied Electrochem. 20, 1990, 338-340.
- [xxxiv] S. Anandhakumar, R. Sripriya, M. Chandrasekaran, S. Govindu, M. Noel, Electrocarboxylation and related radical coupling processes of aryl and benzyl halides in microemulsion, J. Applied Electrochem. 39, 2009, 463-465.
- [xxxv] J-F. Fauverque, A. Jutand, M. François, Nickel catalysed electrosynthesis of anti-inflammatory agents. Part I – Synthesis of aryl-2-propionic acids under galvanostatic conditions, J. Applied Electrochem. 18, 1988, 109-115.
- [xxxvi] M. Tokuda, T. Kabuki, Y. Katoh, H. Suginome, Regioselective synthesis of b,g-unsaturated acids by the electrochemical carboxylation of allylic bromides using a reactive-metal anode, Tetrahedron Lett. 36, 1995, 3345-3348.
- [xxxvii] MH. Kamekawa, H. Senboku, M. Tokuda, Facile synthesis of aryl-substituted 2-alkenoic acids by electroreductive carboxylation of vinylic bromides using a magnesium anode, Electrochem. Acta 42, 1997, 2117-2123.
- [xxxviii] H. Senboku, Y. Fujimura, H. Kamekawa, M. Tokuda, Divergent electrochemical carboxylation of vinyl triflates: new electrochemical synthesis of phenyl-substituted a,b-unsaturated carboxylic acids and aliphatic b-keto carboxylic acids, Electrochem. Acta 45, 2000, 2995-3003.
- [xxxix] H. Kamekawa, H. Senboku, M. Tokuda, New electrochemical carboxylation of vinyl triflates. Synthesis of b-keto carboxylic acids, Tetrahedron Lett. 39, 1998, 1591-1594.
- [xl] H. Senboku, H. Kanaya, Y. Fujimura, M. Tokuda, Stereochemical study on electrochemical carboxylation of vinyl triflates, J. Electroanal. Chem. 507, 2001, 82-88.
- [xli] H.M. Feroci, M. Orsini, L. Rossi, G. Sotgiu, A. Inesi, Electrochemically promoted C-N bond formation from amines and CO2in ionic liquid BMIm-BF4: Synthesis of carbamates, J. Org. Chem. 72, 2007, 200-203.
- [xlii] R.R. Raju, S.K. Mohan, S.J. Reddy, Electroorganic synthesis of 6-aminonicotinic acid from 2-amino-5-chloropyridine, Tetrahedron Lett. 44, 2003, 4133-4135.
- [xliii] A. Gennaro, C.M. Sanchez-Sanchez, A.A. Isse, V. Montiel, Electrocatalytic synthesis of 6-aminonicotinic acid at silver cathodes under mild conditions, Electrochem. Commun. 6, 2004, 627-631.