10.1002/anie.201904568
Angewandte Chemie International Edition
COMMUNICATION
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can deduce that the heterolytic H2 dissociation pathway on the
SFLP of rh-In2O3-x(OH)y is most favored.
The absence of any changes to the optical absorption edge and
lack of any absorption in the visible to near infrared spectral
range of rh-In2O3-x(OH)y, following exposure to H2 at room
temperature, implies that its electronic band structure is hardly
perturbed (Figure S5).[12] This observation supports the
heterolysis model with maintenance of proton-hydride charge-
balance and diamagnetism. Evidence for the latter deduction
stems from the lack of any EPR signals diagnostic of unpaired
electrons localized on the indium sites, trapped in oxygen
vacancies or delocalized in conduction band states (Figure S6).
A few points worth mentioning that provide additional support for
the heterolysis model, described in detail in a forthcoming paper,
include the notable air stability of the H2 treated rh-In2O3-x(OH)y,
the formation of both bicarbonate and formate with CO2,
production of formyl with CO, and reaction with C2H4 to form a
surface ethyl functional group.
In conclusion, the accrued results of a suite of five insightful
spectroscopy probes, DRIFTS, XPS, 1H MAS NMR, EPR and
UV-Vis-NIR, have provided a new window into how gaseous H2
interacts with nanostructured rh-In2O3-x(OH)y at room
temperature. Conclusions drawn from the integrated information
derived from these analytical techniques lean towards the
heterolysis over the homolysis reaction pathway. Inelastic
neutron scattering and extended X-ray absorption fine structure
studies, taken in conjunction with H-D kinetic isotope
measurements, could provide additional structure and reactivity
detail about the surface chemistry of the FLP in rh-In2O3-x(OH)y.
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Acknowledgements
GAO acknowledges the financial support of the Ontario Ministry
of Research and Innovation (MRI), the Ministry of Economic
Development, Employment and Infrastructure (MEDI), the
Ministry of the Environment and Climate Change’s (MOECC)
and the Best in Science (BIS) Award. Acknowledged is
additional support from the Ontario Center of Excellence (OCE)
Solutions 2030 Challenge Fund, the Low Carbon Innovation
Fund (LCIF), Imperial Oil, the University of Toronto Connaught
Innovation Fund (CIF), the Connaught Global Challenge (CGC)
Fund, and the Natural Sciences and Engineering Research
Council of Canada (NSERC). T.Y. is thankful for financial
support from the National Natural Science Foundation of China
(21872081), Natural Science Foundation of Shandong Province
(ZR2016BM04), and the Open Project Program of the State Key
Laboratory of Photocatalysis on Energy and Environment (Grant
No. SKLPEE-KF201711).
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Keywords: Surface frustrated Lewis pair • Heterolytic H2
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