TY - JOUR

T1 - CO2 activation on ultrathin ZrO2 film by H2O co-adsorption

T2 - In situ NAP-XPS and IRAS studies

AU - Li, Hao

AU - Rameshan, Christoph

AU - Bukhtiyarov, Andrey V.

AU - Prosvirin, Igor P.

AU - Bukhtiyarov, Valerii I.

AU - Rupprechter, Günther

N1 - Publisher Copyright: © 2018 The Authors

PY - 2019/1

Y1 - 2019/1

N2 - Utilizing CO2 as sustainable carbon source requires its activation by catalytically active oxides on which CO2 can form different surface bound carbonaceous species. This may be promoted or even enabled by surface hydroxyl groups. We have investigated the interaction of CO2 with a ZrO2 model surface, i.e. a O-Zr-O trilayer grown on Pt3Zr(0001), in the absence and presence of H2O, employing in situ near ambient (atmospheric) pressure X-ray photoemission spectroscopy (NAP-XPS) and infrared reflection absorption spectroscopy (IRAS). Whereas room temperature exposure to pure CO2 up to 3 × 10− 2 mbar did not induce any interaction with the ZrO2 model surface, co-adsorption of CO2 + H2O resulted in the formation of various carbonaceous surface species. Apparently, in the presence of humidity (surface hydroxylation) CO2 was activated on ZrO2 at near ambient pressures. Combining NAP-XPS and IRAS allowed identifying the surface species, which were formate, dioxymethylene, formaldehyde and carbon. These species may be intermediates of upconverting CO2 to methanol and highlight the ability of ZrO2 as active support.

AB - Utilizing CO2 as sustainable carbon source requires its activation by catalytically active oxides on which CO2 can form different surface bound carbonaceous species. This may be promoted or even enabled by surface hydroxyl groups. We have investigated the interaction of CO2 with a ZrO2 model surface, i.e. a O-Zr-O trilayer grown on Pt3Zr(0001), in the absence and presence of H2O, employing in situ near ambient (atmospheric) pressure X-ray photoemission spectroscopy (NAP-XPS) and infrared reflection absorption spectroscopy (IRAS). Whereas room temperature exposure to pure CO2 up to 3 × 10− 2 mbar did not induce any interaction with the ZrO2 model surface, co-adsorption of CO2 + H2O resulted in the formation of various carbonaceous surface species. Apparently, in the presence of humidity (surface hydroxylation) CO2 was activated on ZrO2 at near ambient pressures. Combining NAP-XPS and IRAS allowed identifying the surface species, which were formate, dioxymethylene, formaldehyde and carbon. These species may be intermediates of upconverting CO2 to methanol and highlight the ability of ZrO2 as active support.

KW - CO activation

KW - Dioxymethylene

KW - Formaldehyde

KW - Formate

KW - HO co-adsorption

KW - ZrO ultrathin film

UR - http://www.scopus.com/inward/record.url?scp=85053305022&partnerID=8YFLogxK

U2 - 10.1016/j.susc.2018.08.028

DO - 10.1016/j.susc.2018.08.028

M3 - Article

AN - SCOPUS:85053305022

VL - 679.2019

SP - 139

EP - 146

JO - Surface Science

JF - Surface Science

SN - 0039-6028

IS - January

ER -