Unusual Properties of Oxides and Other Insulators in the Ultrathin Limit

Giordano, Livia; Pacchioni, Gianfranco

doi:10.1002/9783527640171.ch4

Cited by 2 publications

(2 citation statements)

References 86 publications

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“…Thus, a gas-phase approach as in CO 2 GR allows the provision of water to be limited, thus favoring the formation of multicarbon species. − , This multicarbon selectivity is possible by controlling the potential to limit side reactions of protons or electron recombination and, at the same time, to avoid the excessive reduction of the FeOOH, which would lead to a selective state for the HER. We also consider that the extent of the dissolution of atomic C should be limited to the topmost atomic layers of the Fe phase to prevent the formation of a more stable carbide, which would be active for the HER . A partially reduced thin layer of Fe(II) oxide in which lattice O atoms coexists with C atoms is an ideal phase where the N functionalization plays a crucial role in both stabilizing this structure and preventing phase transformation into HER active phases.…”

Section: Resultssupporting

confidence: 89%

Dynamics at Polarized Carbon Dioxide–Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation

et al. 2021

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Surface-sensitive ambient pressure X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy combined with an electrocatalytic reactivity study, multilength-scale electron microscopy, and theoretical modeling provide insights into the gas-phase selective reduction of carbon dioxide to isopropanol on a nitrogen-doped carbonsupported iron oxyhydroxide electrocatalyst. Dissolved atomic carbon forms at relevant potentials for carbon dioxide reduction from the reduction of carbon monoxide chemisorbed on the surface of the ferrihydrite-like phase. Theoretical modeling reveals that the ferrihydrite structure allows vicinal chemisorbed carbon monoxide in the appropriate geometrical arrangement for coupling. Based on our observations, we suggest a mechanism of three-carbon-atom product formation, which involves the intermediate formation of atomic carbon that undergoes hydrogenation in the presence of hydrogen cations upon cathodic polarization. This mechanism is effective only in the case of thin ferrihydrite-like nanostructures coordinated at the edge planes of the graphitic support, where nitrogen edge sites stabilize these species and lower the overpotential for the reaction. Larger ferrihydrite-like nanoparticles are ineffective for electron transport.

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Section: Resultssupporting

confidence: 89%

Dynamics at Polarized Carbon Dioxide–Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation

et al. 2021

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“…The thickness used in this work (1.1nm) falls into the range of native oxide thickness with corresponding reasonable bandgap of 4.9eV, in agreement with literature values. Besides, bandgap of bulk Al 2 O 3 was reported to be around 7∼9eV, 24 much higher than that of the thin oxide film studied in this work. 2.…”

Section: Band Gap Of Thin α-Al 2 O 3 Layer-it Has Previously Been Rep...mentioning

confidence: 53%

A DFT-Study of Cl Ingress into α-Al₂O₃(0001) and Al(111) and Its Possible Influence on Localized Corrosion of Al

Liu

Jin

Leygraf

et al. 2019

J. Electrochem. Soc.

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Ingress of chloride into α-Al 2 O 3 (0001) and Al(111) was calculated by first-principles theory calculations by considering Cl insertion into Al or O vacancies within α-Al 2 O 3 (0001) or into vacancy or interstitial sites within Al(111). For α-Al 2 O 3 , the formation of an O vacancy is energetically more favorable than of an Al vacancy. The insertion of Cl into an O vacancy is also more favorable than into an Al vacancy. A high energy-barrier has been derived for Cl transport within the neighboring O vacancies. In addition, the work function decreases with Cl ingress into the interior of the oxide. For Al(111), Cl insertion into either an Al vacancy or an interstitial site is less favorable compared to the insertion into α-Al 2 O 3 . The work function only changes slightly with Cl insertion into an Al vacancy. Moreover, the pre-inserted Cl reduces the energy-barrier for further Cl ingress into α-Al 2 O 3 , whereas Cl tends to stay in the sub-surface layer of Al(111), suggesting Cl accumulation at the Al 2 O 3 /Al.

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Unusual Properties of Oxides and Other Insulators in the Ultrathin Limit

Cited by 2 publications

References 86 publications

Dynamics at Polarized Carbon Dioxide–Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation

Dynamics at Polarized Carbon Dioxide–Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation

A DFT-Study of Cl Ingress into α-Al₂O₃(0001) and Al(111) and Its Possible Influence on Localized Corrosion of Al

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Unusual Properties of Oxides and Other Insulators in the Ultrathin Limit

Cited by 2 publications

References 86 publications

Dynamics at Polarized Carbon Dioxide–Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation

Dynamics at Polarized Carbon Dioxide–Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation

A DFT-Study of Cl Ingress into α-Al2O3(0001) and Al(111) and Its Possible Influence on Localized Corrosion of Al

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A DFT-Study of Cl Ingress into α-Al₂O₃(0001) and Al(111) and Its Possible Influence on Localized Corrosion of Al