Carbon Dioxide Activation and Reaction Induced by Electron Transfer at an Oxide-Metal Interface

• Published in: Angewandte Chemie International Edition Vol. 54; no. 42; pp. 12484 - 12487
• Main Authors: Calaza, Florencia, Stiehler, Christian, Fujimori, Yuichi, Sterrer, Martin, Beeg, Sebastian, Ruiz-Oses, Miguel, Nilius, Niklas, Heyde, Markus, Parviainen, Teemu, Honkala, Karoliina, Häkkinen, Hannu, Freund, Hans-Joachim
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 12.10.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Activation; Atomic structure; Carbon dioxide; Density; electron transfer; Formations; Infrared radiation; metal-insulator-metal structure; oxalate; Oxalates; oxygen; Radicals; Scanning tunneling microscopy; carbon dioxide; electron transfer; metal-insulator-metal structure; oxalate; oxygen
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201501420

A model system has been created to shuttle electrons through a metal–insulator–metal (MIM) structure to induce the formation of a CO2 anion radical from adsorbed gas‐phase carbon dioxide that subsequently reacts to form an oxalate species. The process is completely reversible, and thus allows the elementary steps involved to be studied at the atomic level. The oxalate species at the MIM interface have been identified locally by scanning tunneling microscopy, chemically by IR spectroscopy, and their formation verified by density functional calculations. Electrons are shuttled back and forth between CO2 and a metal–insulator–metal model system, enabling the activation of CO2 and its reaction to oxalate. This may either react further or reversibly decompose to CO2.