title: Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis.
abstract: Active sites in carbon-catalyzed phosgene synthesis from gaseous CO and Cl2 have been identified using C60 fullerene as a model catalyst. The carbon atoms distorted from sp(2) coordination in non-planar carbon units are concluded to generate active Cl2 . Experiments and density functional theory calculations indicate the formation of a surface-bound [C60 ⋅⋅⋅Cl2 ] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two-step Eley-Rideal-type mechanism.
authors.affiliation: Technische Universität München, Department of Chemistry and Catalysis Research Center, Lichtenbergstrasse 4, 85748, Garching, Germany.
authors.forename: Navneet K
authors.identifier: http://orcid.org/0000-0002-4204-4680
authors.initials: NK
authors.lastname: Gupta
authors.affiliation: Technische Universität München, Department of Chemistry and Catalysis Research Center, Lichtenbergstrasse 4, 85748, Garching, Germany.
authors.forename: Anastasia
authors.identifier: http://orcid.org/0000-0002-5272-6001
authors.initials: A
authors.lastname: Pashigreva
authors.affiliation: Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands. e.a.pidko@tue.nl.|Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands. e.a.pidko@tue.nl.
authors.forename: Evgeny A
authors.identifier: http://orcid.org/0000-0001-9242-9901
authors.initials: EA
authors.lastname: Pidko
authors.affiliation: Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands.
authors.forename: Emiel J M
authors.identifier: http://orcid.org/0000-0002-9754-2417
authors.initials: EJ
authors.lastname: Hensen
authors.affiliation: Technology Development, Bayer Technology Services GmbH, 51368, Leverkusen, Germany.
authors.forename: Leslaw
authors.identifier: http://orcid.org/0000-0002-9039-1310
authors.initials: L
authors.lastname: Mleczko
authors.affiliation: Technology Development, Bayer Technology Services GmbH, 51368, Leverkusen, Germany. stefan.roggan@bayer.com.
authors.forename: Stefan
authors.identifier: http://orcid.org/0000-0002-8574-2040
authors.initials: S
authors.lastname: Roggan
authors.affiliation: Technische Universität München, Department of Chemistry and Catalysis Research Center, Lichtenbergstrasse 4, 85748, Garching, Germany. erika.ember@mytum.de.
authors.forename: Erika E
authors.identifier: http://orcid.org/0000-0003-3800-814X
authors.initials: EE
authors.lastname: Ember
authors.affiliation: Technische Universität München, Department of Chemistry and Catalysis Research Center, Lichtenbergstrasse 4, 85748, Garching, Germany. johannes.lercher@ch.tum.de.
authors.forename: Johannes A
authors.initials: JA
authors.lastname: Lercher
keywords: chlorine; density functional calculations; fullerenes; phosgene; reaction mechanisms