Issue 30, 2012

Preparation and characterization of ultrathin [Ru(CO)3Cl2]2 and [BMIM][Tf2N] films on Al2O3/NiAl(110) under UHV conditions

Abstract

Towards a better understanding of the interface chemistry of ionic liquid (IL) thin film catalytic systems we have applied a rigorous surface science model approach. For the first time, a model homogeneous catalyst has been prepared under ultrahigh vacuum conditions. The catalyst, di-μ-chlorobis(chlorotricarbonylruthenium) [Ru(CO)3Cl2]2, and the solvent, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][Tf2N], have been deposited by physical vapor deposition onto an alumina model support [Al2O3/NiAl(110)]. First, the interaction between thin films of [Ru(CO)3Cl2]2 and the support is investigated. Then, the ruthenium complex is co-deposited with the IL and the influence of the solvent on the catalyst is discussed. D2O, which is a model reactant, is further added. Growth, surface interactions, and mutual interactions in the thin films are studied with IRAS in combination with density functional (DFT) calculations. At 105 K, molecular adsorption of [Ru(CO)3Cl2]2 is observed on Al2O3/NiAl(110). The IRAS spectra of the binary [Ru(CO)3Cl2]2 + [BMIM][Tf2N] and ternary [Ru(CO)3Cl2]2 + [BMIM][Tf2N] + D2O show every characteristic band of the individual components. Above 223 K, partial decomposition of the ruthenium complex leads to species of molecular nature attributed to Ru(CO) and Ru(CO)2 surface species. Formation of metallic ruthenium clusters occurs above 300 K and the model catalyst decomposes further at higher temperatures. Neither the presence of the IL nor of D2O prevents this partial decomposition of [Ru(CO)3Cl2]2 on alumina.

Graphical abstract: Preparation and characterization of ultrathin [Ru(CO)3Cl2]2 and [BMIM][Tf2N] films on Al2O3/NiAl(110) under UHV conditions

Supplementary files

Article information

Article type
Paper
Submitted
05 Mar 2012
Accepted
28 May 2012
First published
29 May 2012

Phys. Chem. Chem. Phys., 2012,14, 10603-10612

Preparation and characterization of ultrathin [Ru(CO)3Cl2]2 and [BMIM][Tf2N] films on Al2O3/NiAl(110) under UHV conditions

M. Sobota, S. Schernich, H. Schulz, W. Hieringer, N. Paape, P. Wasserscheid, A. Görling, M. Laurin and J. Libuda, Phys. Chem. Chem. Phys., 2012, 14, 10603 DOI: 10.1039/C2CP40697G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements