caa a22 4500 606173285 CHVBK 20210128100732.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s11244-014-0343-z doi (NATIONALLICENCE)springer-10.1007/s11244-014-0343-z Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights [Elektronische Daten] [Emily Barton Cole, Maor Baruch, Robert L'Esperance, Michael Kelly, Prasad Lakkaraju, Elizabeth Zeitler, Andrew Bocarsly] A series of substituted pyridiniums were examined for their catalytic ability to electrochemically reduce carbon dioxide to methanol. It is found that in general increased basicity of the nitrogen of the amine and higher LUMO energy of the pyridinium correlate with enhanced carbon dioxide reduction. The highest faradaic yield for methanol production at a platinum electrode was 39±4% for 4-aminopyridine compared to 22±2% for pyridine. However, 4-tertbutyl and 4-dimethylamino pyridine showed decreased catalytic behavior, contrary to the enhanced activity associated with the increased basicity and LUMO energy, and suggesting that steric effects also play a significant role in the behavior of pyridinium electrocatalysts. Mechanistic models for the the reaction of the pyridinium with carbon dioxide are considered. Springer Science+Business Media New York, 2014 Pyridinium catalyzed CO2 Reduction nationallicence CO2 to methanol conversion nationallicence Electrochemical CO2 reduction nationallicence Barton Cole Emily Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut Baruch Maor Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut L'Esperance Robert Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut Kelly Michael Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut Lakkaraju Prasad Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut Zeitler Elizabeth Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut Bocarsly Andrew Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/1(2015-02-01), 15-22 1022-5528 58:1<15 2015 58 11244 https://doi.org/10.1007/s11244-014-0343-z text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-014-0343-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Barton Cole Emily Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Baruch Maor Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- L'Esperance Robert Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Kelly Michael Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Lakkaraju Prasad Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Zeitler Elizabeth Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Bocarsly Andrew Frick Chemical Laboratory, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/1(2015-02-01), 15-22 1022-5528 58:1<15 2015 58 11244