1. Leah G. Dodson, Michael C. Thompson, J. Mathias Weber
Infrared photodissociation cluster studies on CO2 interaction with titanium oxide catalyst models
Leah G. Dodson, Michael C. Thompson, J. Mathias Weber
JILA, NIST, and Department of Chemistry and Biochemistry
University of Colorado, Boulder, Colorado
72nd International Symposium on Molecular Spectroscopy
June 21, 2017
WD10

2. TiO2 Surface Modification by CO2
carboxylic acid anchors on TiOx
introduction of band-tail states by bidentate CO2 ligands
Zhang and Cole, ACS Appl. Mater. Interfaces 2015, 7,3427.
Ma et al., Cat. Comm. 2017, 95, 1.

3. Metal-CO2 Anionic Cluster Binding Motifs
Co, Ni, Cu,
Mn, Fe
Bi, Mn, Fe
Mn, Fe
Au, Ag, Cu, Bi
Co, Ni, Fe Fe
Knurr and Weber, J. Am. Chem. Soc. 2012, 134,
Knurr and Weber, J. Phys. Chem. A 2013, 117,
Knurr and Weber, J. Phys. Chem. A 2014, 118, 4056.
Knurr and Weber, J. Phys. Chem. A 2014, 118, 8753.
Miller et al., Angew. Chem. Int. Ed. 2014, 53,
Thompson et al., Angew. Chem. Int. Ed. 2016, 55,
Thompson et al., J. Phys. Chem. A 2017, 121, 4132.
*Titanium: Oxophilic, Small

4. Ligand Formation in [TiOx(CO2)y]− Clusters
Titanium: good at stabilizing highly unstable ligands (carbonate, oxalate). Highly oxophilic: metal-oxygen bond formation.
Carbonate Ligand
Ti, TiO, TiO2, TiO3
η2-(O,O) Carbene Ligand
TiO, TiO2
η2-(C,O) Bidentate Ligand
TiO2
Oxalate Ligand
Ti, TiO
Carbonyl Ligand (Insertion Structures)
carbonate
η2-(O,O) carbene
η2-(C,O) bidentate
oxalate
carbonyl

5. Infrared Photodissociation Spectroscopy
Mass Selection
Photodissociation
Reflectron TOF
950–2400 cm−1
[TiOx∙(CO2)y]−
Laser ablation
CO2 expansion Ti
CO2
[TiO2∙(CO2)3]− + hν
[TiO2∙(CO2)3]−
[TiO2∙(CO2)3]− + hν  [TiO2∙(CO2)2]− + CO2

6. Data unpublished at time of archiving
Data unpublished at time of archiving. They may be restored to this file after publication.

7. Summary Titanium stabilizes diverse ligand structures
Carbonate ligands present in all TiOx (x = 0–3)
Bidentate CO2 ligands (η2-(C,O) and η2-(O,O))
High degrees of coordination

8. Research Associateship
Acknowledgements
NSF AMO
PFC
NIST NRC
Research Associateship