A Gas Phase Investigation Of Cuoh(h2o)+ And Cu(ii) Oligoglycine Water Oxidation Catalysts

Marsh, Brett

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https://hdl.handle.net/2142/50916 Copy

Description

Title

A Gas Phase Investigation Of Cuoh(h2o)+ And Cu(ii) Oligoglycine Water Oxidation Catalysts

Author(s)

Marsh, Brett

Contributor(s)

• Garand, Etienne
• Zhou, Jia

Issue Date

2014-06-17

Keyword(s)

Mini-symposium: Beyond the Mass-to-Charge Ratio: Spectroscopic Probes of the Structures of Ions

Abstract

The abundance of copper and copper compounds within the crust of the Earth and the well characterized coordination chemistry of copper species has led to investigation of copper as a catalyst for several different chemical reactions. Among the most notable of these has been the application of copper containing compounds to water oxidation. The chemistry used in this reaction has thus far been dominated by expensive materials containing the rare metals ruthenium or iridium. In this presentation we study several copper species which have attracted interest in this field including CuOH(\chem{H_2O})$_{n}$$^{+}$ clusters and Cu(II) oligoglycine complexes. We find that in the case of CuOH(\chem{H_2O})$_{n}$$^{+}$ clusters that the undercoordinated CuOH(\chem{H_2O})$^{+}$ cluster has a strong affinity towards activating D$_{2}$ while the higher coordinated CuOH(\chem{H_2O})$_{2}$$^{+}$ and CuOH(\chem{H_2O})$_{3}$$^{+}$ clusters show no propensity for the activation of D$_{2}$. In the case of the Cu(II) oligoglycine complexes we find that the charge environment strongly affects the diagnostic CO stretch frequencies, creating a clear spectroscopic fingerprint for assessing the charge and interactions within these systems. Despite the small size (6-12 atoms) of the CuOH(\chem{H_2O})$_{n}$$^{+}$ clusters electronic structure methods including DFT and MP2 give poor agreement with the experimental results while DFT calculations on the relatively large Cu(II) oligoglycine species show excellent agreement with experiment.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/50916

DOI

https://doi.org/10.15278/isms.2014.TG13

Copyright and License Information

Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/

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