CO2 Valorization

Background

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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.

Possible ways of CO2 Valorization: Capture, storage and use as chemical feed_stock. The activation of carbon_dioxide is crucial 

Since COis a source of carbon it could be considered as an attractive building block for chemistry given its low cost and abundance. Unfortunately, COis 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 COis currently being used for chemical synthesis, which is mainly caused by its chemical inertness and the high costs of COcapture 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 CObut those processes are not selective enough to transform COin more sophisticated molecules, such as fine chemicals or pharmaceutical agents. Furthermore, COcan 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 COto 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]].


Our Project

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 COwhich 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.

CO2 Valorizationneeds to achive an understanding of carbon_dioxide activation. Experiments and simulations are needed

Our goal is to achieve understanding of the activation of COtowards 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.


Our Capabilities

High pressure rotating disc electrochemical reactor (HPRDE-100 , yashentech). 

Features:

  • 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

HPRDE-100: High pressure electrochemical Reactor that alowes to stdudy CO2 valorization reactions 

Theoretical Capabilities

  • 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


Own Publications

Capture & Separation:

  1. "Modelling the HCOOH/COElectrochemical Couple: When Details Are Key", S. Steinmann, C. Michel, R. Schwiedernoch, J.-S. Filhol, P. Sautet; ChemPhysChem, Article first published online: 10 JUN 2015
    (DOI: http://dx.doi.org/10.1002/cphc.201500187

  2. 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.  
    (DOI: http://dx.doi.org/10.1039/c5cp00946d)

  3. “Formation of acrylates from ethylene and COon 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.  
    (DOI: http://dx.doi.org/10.1021/om5006808)
        Wenping Guo, Organometallics 2014, in press 

  4. "Porous Inorganic Membranes for COcapture: present and prospects", M. Pera-Titus, Chem. Rev, (2014), 114 (2), 1413–1492.
    (DOI: http://dx.doi.org/10.1021/cr400237k
        M. Pera-Titus, Chem. Rev. (2014), 114(2), p.1413 CO2 capture 

  5. "Nanocomposite MFI-Alumina Hollow Fiber Membranes: Influence of NOand Propane on CO2/NSeparation Properties", C-H. Nicolas, M. Pera-Titus; Ind. Eng. Chem. Res. 51 (2012),10451-10461.
    (DOI:  http://dx.doi.org/10.1021/ie300925m)


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