Discriminating the Role of Surface Hydride and Hydroxyl for Acetylene Semihydrogenation over Ceria through In Situ Neutron and Infrared Spectroscopy

Moon, Jisue; Cheng, Yongqiang; Daemen, Luke L.; Li, Meijun; Polo Garzon, Felipe; Ramirez Cuesta, Anibal; Wu, Zili

doi:10.1021/acscatal.0c00808

Discriminating the Role of Surface Hydride and Hydroxyl for Acetylene Semihydrogenation over Ceria through In Situ Neutron and Infrared Spectroscopy

Journal Article · Wed Apr 08 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c00808· OSTI ID:1649427

Moon, Jisue ^[1]; ^[2]; Daemen, Luke L. ^[2]; ^[1]; ^[1]; ^[2]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division

Ceria has been used as a hydrogenation catalyst especially in selective alkyne hydrogenation, but the reaction mechanism regarding the role of different surface hydrogen species remains unclear. Here, we utilized in situ neutron and infrared vibration spectroscopy to show the catalytic role of cerium hydride (Ce–H) and hydroxyl (OH) groups in acetylene hydrogenation over ceria surfaces with different degree of reduction. In situ inelastic neutron scattering spectroscopy (INS) proved that not only Ce–H but also surface atomic hydrogen species on the reduced ceria surface can participate in acetylene semihydrogenation. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results implied that bridging OH groups both on the oxidized and reduced ceria are active in the selective hydrogenation of acetylene. It appears that surface Ce–H is more reactive than the coexisting OH species on the reduced ceria surface, but over-reduction of ceria also results in strongly bound species that may lead to catalyst deactivation. These spectroscopic results clearly explain the reaction mechanism including not only the surface chemistry but also the nature of the active hydrogen species for selective hydrogenation over ceria, providing insights into the design of more active and stable ceria-based catalysts for hydrogenation reactions.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1649427

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 9 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
IR spectroscopy
acetylene
ceria
hydride
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inelastic neutron scattering
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Discriminating the Role of Surface Hydride and Hydroxyl for Acetylene Semihydrogenation over Ceria through In Situ Neutron and Infrared Spectroscopy

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