AP-XPS Study of the Reaction of O2 and CO2 with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO

Mehar, Vikram; Kim, Jeongjin; Hunt, Adrian; Waluyo, Iradwikanari; Rodriguez, José A.

doi:10.1021/acs.jpcc.4c03321

AP-XPS Study of the Reaction of O₂ and CO₂ with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO

Journal Article · Tue Aug 13 00:00:00 EDT 2024 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.4c03321· OSTI ID:2440526

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Brookhaven National Laboratory (BNL), Upton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of). Pohang Light Source II
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the dissociation of O₂ and CO₂ on Zn-Au(111) alloys which contained 0.2-0.3 monolayers of zinc. Although Au(111) is inert, the alloys displayed a high activity for the cleavages of O-O and C-O bonds at room temperature with the formation of ZnO_x species. Dissociative adsorption of O₂ at 300 K destroyed the alloys and the results of AP-XPS pointed to the co-existence of two types of oxygen species on the surface: ZnO_x and chemisorbed O atoms (O_chem) on Au or the Au-ZnO interface. Annealing from room temperature to 600 K induced a O_chem → ZnO_x transformation that reflected the poor stability of O atoms on Au(111). The Zn-Au(111) systems exhibited a reactivity towards CO₂ that was much larger than that seen for Au(111), Cu(111) or surfaces of late transition metals like, Ni, Pd or Pt. At 300 K, CO₂ underwent partial dissociation depositing large amounts of O_chem on the surface with minor formation of ZnO_x. In addition, the deposited O_chem reacted with CO₂ to form surface carbonate groups. Dosing of CO₂ at 500-600 K mainly led to the formation of ZnO_x and the surface carbonate almost disappeared. In the presence of hydrogen, i.e. reaction feeds with a CO₂ to H₂ ratio of 1:3, the surface chemistry at 300 K was very similar to that seen for pure CO₂ with the formation of ZnO_x and carbonate groups. In contrast, at 500-600 K, reaction with hydrogen induced the removal of ZnO_x and CO₃/HCOO species. Finally, our AP-XPS results are consistent with the idea that CO₂ hydrogenation on AuZn alloys involves a redox process where there is sequential oxidation by CO₂ and reduction by H₂ to yield methanol.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0012704

OSTI ID:: 2440526

Report Number(s):: BNL--226053-2024-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 33 Vol. 128; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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AP-XPS Study of the Reaction of O₂ and CO₂ with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO