Activation of carbon dioxide at bismuth, gold and copper surfaces

Browne, V.M.; Carley, Albert Frederick; Copperthwaite, Richard G.; Davies, Philip R.; Moser, E. M.; Roberts, M. W.

doi:10.1016/0169-4332(91)90091-w

Cited by 38 publications

(29 citation statements)

References 12 publications

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“…For physisorbed CO 2 on Cu(111), we have obtained a theoretical C1s binding energy shift of 4.92 eV. Favaro et al [12] have reported a binding energy shift of 3.4 eV for CO 2 on Cu(111), but the binding energy shifts reported for physisorbed CO 2 on other Cu surfaces and polycrystalline copper are significantly larger and range from 6.0 eV to 7.0 eV [18][19][20]. Similarly large shifts of 6.2 eV and 6.5 eV have been reported for physisorbed CO 2 on Ni(110) and polycrystalline iron [75], respectively.…”

Section: Results: Adsorbates On Cu(111)mentioning

confidence: 96%

Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Kahk

Lischner

2018

Phys. Chem. Chem. Phys.

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Core-level X-ray Photoelectron Spectroscopy (XPS) is often used to study the surfaces of heterogeneous copper-based catalysts, but the interpretation of measured spectra, in particular the assignment of peaks to adsorbed species, can be extremely challenging. In this study we demonstrate that first principles calculations using the delta Self Consistent Field (delta-SCF) method can be used to guide the analysis of experimental core level spectra of complex surfaces relevant to heterogeneous catalysis. Specifically, we calculate core-level binding energy shifts for a series of adsorbates on Cu(111) and show that the resulting C1s and O1s binding energy shifts for adsorbed CO, CO2, C2H4, HCOO, CH3O, H2O, OH, and a surface oxide on Cu(111) are in good overall agreement with the experimental literature. In the few cases where the agreement is less good, the theoretical results may indicate the need to re-examine experimental peak assignments.

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Section: Results: Adsorbates On Cu(111)mentioning

confidence: 96%

Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Kahk

Lischner

2018

Phys. Chem. Chem. Phys.

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“…Alternatively, adsorbed CO 2 on metallic surfaces has been observed at binding energies close to this. 6,7 The significantly lower intensity of these oxidized carbon groups after the higher pressure exposure (see Table 2) suggests that the groups are adsorbed at the carbon/metal oxide interface and become more obscured by the thicker carbonaceous layer at higher pressure. Other carbon species are observed in the spectra in Fig.…”

Section: Surface Reactions Of Co 2 (G) On Clean Iron: Xps Studiesmentioning

confidence: 93%

Interactions of CO₂ and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination?

Miller

Biesinger

McIntyre

2002

Surface & Interface Analysis

250

156

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The interactions of carbon dioxide and carbon monoxide at moderately high pressures with clean iron surfaces have been studied using x-ray photoelectron spectroscopy (XPS) and static time-of-flight secondary ion mass spectrometry (ToF-SIMS). Clean iron surfaces were analysed after exposure to CO 2 or CO gas having pressures of 10-10 4 Pa at 25• C. Exposure to either gas results first in a thin surface film of FeO. In addition, this oxide is completely or partially covered with a carbonaceous layer. The thickness of the carbon layer is influenced by the type of gas used and its pressure. The ToF-SIMS studies using isotopically labelled 13 CO 2 under the same reaction conditions show that the labelled carbon is not enriched on the surface and therefore no direct reaction occurs between the labelled carbon and the surface. It is proposed that the influence of either gas on the carbonaceous layer formed may be indirect: these gases may alter the equilibrium partial pressures of other adsorbates on the walls of the vacuum chamber.

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“…To discriminate between physisorbed and chemisorbed CO2, we monitor the spectral BE shifts of the corresponding C 1s and O 1s photoelectron peaks as a function of the different surfaces and experimental conditions. Physisorption mediated by weak van der Waals (vdW) interactions [surface binding energies of a few millielectronvolts, comparable to kB T = 25.7 meV at 298 K (7)] generally leaves the adsorbate electronic structure unchanged compared with its gas-phase configuration (7,(22)(23)(24). In contrast, the chemical bonding needed to form chemisorbed CO2 on the Cu surface redistributes the electronic density in the adsorbate, leading to appreciable BE shifts compared with the physisorbed state (8).…”

Section: Significancementioning

confidence: 99%

“…S4). This important shift means that an actual interaction is taking place between the adsorbate and the surface (7,22), although the adsorption state still resembles physisorption.…”

Section: Significancementioning

confidence: 99%

Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂

Favaro

Xiao

Cheng

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

417

362

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A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. T he discovery of new electrocatalysts that can efficiently convert carbon dioxide (CO2) into liquid fuels and feedstock chemicals would provide a clear path to creating a sustainable hydrocarbon-based energy cycle (1). However, because CO2 is highly inert, the CO2 reduction reaction (CO2RR) is quite unfavorable thermodynamically. This makes identification of a suitable and scalable catalyst an important challenge for sustainable production of hydrocarbons. We consider that discovering such a catalyst will require the development of a complete atomistic understanding of the adsorption and activation mechanisms involved. Here the first step is to promote initiation of reaction steps.Copper (Cu) is the most promising CO2RR candidate among pure metals, with the unique ability to catalyze formation of valuable hydrocarbons (e.g., methane, ethylene, and ethanol) (2). However, Cu also produces hydrogen, requires too high an overpotential (>1 V) to reduce CO2, and is not selective for desirable hydrocarbon and alcohol CO2RR products (2). Despite numerous experimental and theoretical studies, there remain considerable uncertainties in understanding the role of Cu surface structure and chemistry on the initial steps of CO2RR activity and selectivity (3, 4). To reduce CO2 to valuable hydrocarbons, a source of protons is needed in the same reaction environment (2), with water (H2O) the favorite choice. Thus, H2O is often the solvent for CO2RR, representing a sustainable pathway toward solar energy storage (1). However, we lack a comprehensive understanding of how CO2 and H2O molecules adsorb on the Cu surface and interact to first dissociate the CO2 (5, 6). An overview of the various surface reactions of CO2 on Cu(111) is reported in Fig. 1, illustrating the transient carbon-based intermediate species that may initiate reactions.Previous studies using electron-based spectroscopies observed physisorption of gas-phase g-CO2 at 75 K, whereas a chemisorbed form of CO2 was stabilized by a partial negative charge induced by electron capture (CO δ− 2 ) (Fig. 1A) (7, 8). The same experiments showed th...

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Activation of carbon dioxide at bismuth, gold and copper surfaces

Cited by 38 publications

References 12 publications

Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Interactions of CO₂ and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination?

Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂

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Activation of carbon dioxide at bismuth, gold and copper surfaces

Cited by 38 publications

References 12 publications

Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Interactions of CO2 and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination?

Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2 , the first step in reduction of CO 2

Contact Info

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Interactions of CO₂ and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination?

Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂