TY - JOUR
T1 - CO2 Adsorption on Ti3O6-
T2 - A Novel Carbonate Binding Motif
AU - Debnath, Sreekanta
AU - Song, Xiaowei
AU - Fagiani, Matias R.
AU - Weichman, Marissa L.
AU - Gao, Min
AU - Maeda, Satoshi
AU - Taketsugu, Tetsuya
AU - Schöllkopf, Wieland
AU - Lyalin, Andrey
AU - Neumark, Daniel M.
AU - Asmis, Knut R.
N1 - Funding Information:
This work has been supported by the German Research Foundation (DFG) within the CRC 1109 “Metal Oxide− Water Systems”. X.S. thanks the Alexander-von-Humboldt Foundation for a postdoctoral research fellowship. M.L.W. thanks the National Science Foundation for a graduate research fellowship. D.M.N. thanks the Air Force Office of Scientific Research for funding this research (No. FA9550-16-1-0097). M.G., S.M., T.T., and A.L. are grateful for financial support from the programs of the Ministry of Education, Culture, Sports, Science and Technology (MEXT, Japan) on the “Development of Environmental Technology using Nanotechnology” and “Priority Issue on Post-K computer” (development of new fundamental technologies for high-efficiency energy creation, conversion/storage and use). Institute for Chemical Reaction Design and Discovery (ICRD) was established by World Premier International Research Initiative (WPI), MEXT, Japan. A.L. and T.T. gratefully acknowledge the financial support of JSPS KAKENHI Grant Nos. 15K05387 and 16KT0047, respectively.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2019/4/4
Y1 - 2019/4/4
N2 - CO2 adsorption on Ti3O6-, which serves as a model for an oxygen vacancy on a titania surface, is studied using infrared photodissociation (IRPD) spectroscopy in combination with density functional theory (DFT) and coupled cluster computations, as well as a recently developed multicomponent artificial force induced reaction method. The IRPD spectra of D2-tagged [(Ti3O6)(CO2)n]-, with n = 1, 2, are reported in the spectral window of 450-2400 cm-1 and assigned based on a comparison to harmonic IR spectra from the DFT calculations. We find that CO2 binding leaves the unpaired electron largely unperturbed. The first two CO2 molecules adsorb chemically to Ti3O6- by incorporating a formally doubly negatively charged, either doubly or triply coordinated O atom to form a bidentate or tridentate bridging carbonate dianion (CO32-), respectively. The latter binding motif exhibits a characteristic IR signature in the form of an intense doublet of peaks near 1400 cm-1 stemming from two antisymmetric carbonate stretching modes.
AB - CO2 adsorption on Ti3O6-, which serves as a model for an oxygen vacancy on a titania surface, is studied using infrared photodissociation (IRPD) spectroscopy in combination with density functional theory (DFT) and coupled cluster computations, as well as a recently developed multicomponent artificial force induced reaction method. The IRPD spectra of D2-tagged [(Ti3O6)(CO2)n]-, with n = 1, 2, are reported in the spectral window of 450-2400 cm-1 and assigned based on a comparison to harmonic IR spectra from the DFT calculations. We find that CO2 binding leaves the unpaired electron largely unperturbed. The first two CO2 molecules adsorb chemically to Ti3O6- by incorporating a formally doubly negatively charged, either doubly or triply coordinated O atom to form a bidentate or tridentate bridging carbonate dianion (CO32-), respectively. The latter binding motif exhibits a characteristic IR signature in the form of an intense doublet of peaks near 1400 cm-1 stemming from two antisymmetric carbonate stretching modes.
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U2 - 10.1021/acs.jpcc.8b10724
DO - 10.1021/acs.jpcc.8b10724
M3 - Article
AN - SCOPUS:85063990368
VL - 123
SP - 8439
EP - 8446
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 13
ER -