Transient Studies of CO2 Adsorption over CeO2 Nanostructures with In Situ DRIFTS and Modulation Excitation

Wang, Yuxi; Moncada, Jorge; Sahoo, Sanjubala; Deng, Kaixi; Chen, Xiaobo; Liu, Ping; Zhu, Hongda; Bravo-Suárez, Juan J.; Martínez-Arias, Arturo; Rodriguez, José Antonio

doi:10.1021/acs.jpcc.5c05912

Transient Studies of CO₂ Adsorption over CeO₂ Nanostructures with In Situ DRIFTS and Modulation Excitation

Journal Article · Thu Dec 11 00:00:00 EST 2025 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5c05912· OSTI ID:3010081

^[1]; Moncada, Jorge ^[2]; ^[3]; Deng, Kaixi ^[4]; ^[5]; ^[2]; Zhu, Hongda ^[6]; ^[6]; ^[7]; ^[8]

State Univ. of New York (SUNY), Stony Brook, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Univ. of Connecticut, Storrs, CT (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States); State Univ. of New York (SUNY), Stony Brook, NY (United States)
State Univ. of New York (SUNY), Binghamton, NY (United States)
Univ. of Kansas, Lawrence, KS (United States)
Instituto de Catálisis y Petroleoquímica (ICP-CSIC), Madrid (Spain)
State Univ. of New York (SUNY), Stony Brook, NY (United States)

Experiments of in-situ DRIFTS combined with modulation excitation (ME) spectroscopy showed a rich surface chemistry associated with the adsorption of CO₂ on nanocubes and nanospheres of ceria. The nanocubes exposed faces with a (100) orientation, with the edges and corners displaying (110) and (111) orientations, respectively. Here, the nanospheres mainly contained ceria (111) and (110) planes. DFT calculations showed that CO₂ is a multidentate adsorbate on ceria that can undergo changes in its bonding configuration depending on the chemical environment. At 250 °C, a temperature typically used for the conversion of CO₂ into oxygenates, alkanes and olefins, CO₂ reacted with O centers or OH groups present on the nanocubes and nanospheres to yield bi- and tri-dentate carbonates, hydroxycarbonates, and formates. Both nanostructures were highly reactive and a dynamic equilibrium was established: carbonate species were rapidly generated upon the injection of CO₂ and they decomposed upon the removal of CO₂ from the gas phase. In the case of the ceria nanocubes, the adsorption/desorption processes were essentially reversible, opening the door to catalytic transformations. A larger concentration of defects in the ceria nanospheres led to strongly bound carbonates and formates that may be spectators, site blockers, or surface modifiers in catalytic processes. In the ME studies, additional intermediates were detected, and it was clear that the response of surface species to the presence/absence of CO₂ was highly dependent on the morphology of the ceria nanostructures.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 3010081

Report Number(s):: BNL-229247-2025-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 51 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Transient Studies of CO2 Adsorption over CeO2 Nanostructures with In Situ DRIFTS and Modulation Excitation

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Transient Studies of CO₂ Adsorption over CeO₂ Nanostructures with In Situ DRIFTS and Modulation Excitation