Michael E Goodrich amp David T Moore Chemistry Department Lehigh University Bethlehem PA 18015 1 Introduction CO Oxidation on metal center CuCO m O 2 n complexes difficult to form ID: 213576
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Carbon Dioxide Clusters and Copper Complexes Formed in Argon Matrices
Michael E. Goodrich & David T. MooreChemistry Department, Lehigh UniversityBethlehem PA, 18015
1Slide2
Introduction
CO Oxidation on metal centerCu(CO)m(O2)n complexes difficult to formWhat happens when both CO and CO2 are in the matrixIdentify CO2 species in matrix
Identify Cu(CO)(CO2) clusters
2Slide3
Experimental
3Deposit 0.02-0.5% CO2 in Argon at 10sccm and 10-20K~4 nA beam of Cu- balanced with a 25-50eV cationic counter ion (
Ar+/SF
5+)Slide4
CuCO
2 and CO2
Clusters
4CuCO2-CO2-(CO2-)(CO2)C2O4-10K Deposition of 0.5% CO2 in Argon with Cu- and Ar+Observe conversion of anionic CO2 cluster to oxalate-like C2O4-
No apparent conversion to anionic CO2 peaksZhou, M.; et al. J. Phys. Chem. A. 103, 2013. (1999) Zhou, M.; Andrews, L. J. Chem. Phys. 110, 2414 (1999)Slide5
CO2
Symmetric Stretch Region5
(CO
2)2(CO2)2(CO2)2+CuCO2-10K Deposition of 0.5% CO2 in Argon with Cu- and Ar+Minimal changes upon irradiation and annealingZhou, M.; et al. J. Phys. Chem. A. 103, 2013. (1999) Castano, J.A.G.; et al. J Mol. Structure 881, 68. (2008).Slide6
Effect of Counter Ion Choice on CO
2 cluster formation
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SF5+ shuts down the formation of cationic CO2 clustersNo presence of anionic clusters in SF5+ spectrumHigh energy argon increases formation of cationic CO2 clustersSF6Anionic clusters present upon deposition of Ar+ suggesting formation is necessary for charge balanceSlide7
Matrix Containing CO and CO2
70.02% CO & CO2 deposited at 20K
No presence of CuCO2
-Cu(CO)2CuCO-Cu(CO)2-Cu(CO)3-Cu(CO)3CuCOC2O3-Peaks at 1701 and 1793 cm-1 assigned to C2O3-Zhou, M.; Andrews, L. J. Chem Phys. 111, 4548 (1999) Zhou, M.; et al. J. Chem. Phys. 112, 7089 (2000).Slide8
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Matrix Containing CO and CO2
Small CuCO
2- peak when CO2 concentration is higher than CONo evidence of ternary Cu(CO)(CO2) complexesSlide9
Conclusions and Future Work
Identified Copper Carbon Dioxide Clusters and Ionic Carbon Dioxide clusters in an argon matrixCan control ionization pathways based on counter ion choiceFurther attempts to form Cu(CO)(CO2) clusters and CuCO2 clusters with CO present in matrix
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