% IMPORTANT: The following is UTF-8 encoded.  This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.

@INPROCEEDINGS{Jovanovic:1010210,
      author       = {Jovanovic, Sven and Jakes, Peter and Merz, Steffen and
                      Eichel, Rüdiger-A. and Granwehr, Josef},
      title        = {$\<i\>{I}n$ $operando\</i\>$ {NMR} investigations of
                      electrolyte chemistry during ${CO}\<sub\>2\</sub\>$
                      electrolysis},
      reportid     = {FZJ-2023-03019},
      year         = {2023},
      abstract     = {The electrolytic reduction of CO2 in aqueous media is a
                      powerful method for the large scale utilization of carbon
                      dioxide. There have been large advances in catalyst and cell
                      design, but only little progress has been made regarding in
                      operando and in situ methods for the research of chemical
                      and physical processes taking during electrolysis. NMR
                      spectroscopy is a powerful method for the investigation of
                      chemical systems, and has been applied regularly for the
                      study of catalytically reactions. In general, NMR is thought
                      to be incompatible with electrochemical reactors, i.e.
                      electrolysis cells, due to the distortion of the main
                      magnetic and radio frequency field by conductive cell
                      components. In this study, we overcame these challenges and
                      developed an in operando electrolysis setup which enables
                      NMR investigations of the electrolytic CO2 reduction, which
                      is compatible with standard hardware and pulse sequences.
                      The setup was applied to the examination of physical and
                      chemical properties of solvated CO2 and a commonly used
                      bicarbonate salt electrolyte during three electrochemical
                      stages with increasingly negative potential. In addition to
                      acquiring 13C NMR spectra over course of the electrolysis,
                      T1 and T2 relaxation as well as 1D exchange spectroscopy
                      (EXSY) experiments were utilized in order to learn about the
                      dynamics and equilibrium reactions of the involved species.
                      It was found that in a concentrated electrolyte solution,
                      the electrolyte anions and cations exist both as free ions
                      and ion pairs, where the exchange rate between both forms
                      decreases with increasingly negative potential. The effect
                      of the potential on the exchange rate was confirmed by
                      repeating the experiments at different magnetic field
                      strengths. Furthermore, it was shown via analysis of the
                      relaxation data that solvated CO2 is preferentially in a
                      dynamic equilibrium with bicarbonate anions in form of an
                      ion pair, and that the CO2/bicarbonate equilibrium reaction
                      rate increases with increasingly stable ion pairs in
                      solution. Finally, a catalytic mechanism was proposed on
                      this basis, where the electrolyte cation stabilizes the
                      transition of bicarbonate to CO2 comparable to the enzyme
                      carbonic anhydrase in biological systems.},
      month         = {Jun},
      date          = {2023-06-25},
      organization  = {20th International Conference on
                       Carbon Dioxide Utilization, Bari
                       (Italy), 25 Jun 2023 - 30 Jun 2023},
      subtyp        = {Plenary/Keynote},
      cin          = {IEK-9},
      cid          = {I:(DE-Juel1)IEK-9-20110218},
      pnm          = {1232 - Power-based Fuels and Chemicals (POF4-123) / DFG
                      project 390919832 - EXC 2186: Das Fuel Science Center –
                      Adaptive Umwandlungssysteme für erneuerbare Energie- und
                      Kohlenstoffquellen (390919832)},
      pid          = {G:(DE-HGF)POF4-1232 / G:(GEPRIS)390919832},
      typ          = {PUB:(DE-HGF)6},
      doi          = {10.34734/FZJ-2023-03019},
      url          = {https://juser.fz-juelich.de/record/1010210},
}