The interaction of CO2 with potassium-promoted Cu(100): adsorption, reactions and radiation induced dissociation of CO2

Onsgaard, J.; Storm, J.; Christensen, S.V.; Nerlov, Jesper; Godowski, P. J.; Morgen, Per; Batchelor, David

doi:10.1016/0039-6028(95)00504-8

Cited by 25 publications

(7 citation statements)

References 40 publications

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“…S19C). The proposed assignment of the carboxylate peaks is in good agreement with literature data for alkali metal-CO 2 − and macrocycle-CO 2 − adducts, as well as for *CO 2 − formed on metals and metal oxides from gas phase (16,17,48,49,(63)(64)(65)(66). In particular, the ν as CO 2 − and ν s CO 2 − peaks of *CO 2 − on transition metals have been reported at 1,530-1,660 and 1,130-1,350 cm −1 , respectively, while its δCO 2 − peak, at 650-820 cm −1 (16,17,48).…”

Section: −supporting

confidence: 88%

On the origin of the elusive first intermediate of CO ₂ electroreduction

Чернышова

Somasundaran

Ponnurangam

2018

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

392

332

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We resolve the long-standing controversy about the first step of the CO electroreduction to fuels in aqueous electrolytes by providing direct spectroscopic evidence that the first intermediate of the CO conversion to formate on copper is a carboxylate anion *CO coordinated to the surface through one of its C-O bonds. We identify this intermediate and gain insight into its formation, its chemical and electronic properties, as well as its dependence on the electrode potential by taking advantage of a cutting-edge methodology that includes operando surface-enhanced Raman scattering (SERS) empowered by isotope exchange and electrochemical Stark effects, reaction kinetics (Tafel) analysis, and density functional theory (DFT) simulations. The SERS spectra are measured on an operating Cu surface. These results advance the mechanistic understanding of CO electroreduction and its selectivity to carbon monoxide and formate.

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Section: −supporting

confidence: 88%

On the origin of the elusive first intermediate of CO ₂ electroreduction

Чернышова

Somasundaran

Ponnurangam

2018

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

392

332

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“…This result was also corroborated by HREELS,where peaks associated with physisorbed species at 631 and 2372 cm -1 disappeared at 173 K. Peak identifications, binding energies (eV) and assignments of structures in the photoemission valence spectra. Reproduced with permission from Elsevier[121].The importance of alkali doping on a reaction towards adsorbing CO 2 was illustrated on other surfaces. For example, Pt (111) is an inert surface towards CO 2 that is activated by preadsorbing K on its surface [122][123].…”

mentioning

confidence: 99%

Surface chemistry of carbon dioxide revisited

Taifan

Boily

Baltrušaitis

2016

Surface Science Reports

153

129

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This review discusses modern developments in CO 2 surface chemistry by focusing on the work published since the original review by H. J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO 2 interactions thereon. While UHV spectroscopy has routinely been applied for CO 2 gas-solid interface analysis, the present work goes further by describing surface-CO 2 interactions under elevated CO 2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes salient in situ techniques relevant to the resolution of the interfacial chemistry of CO 2 , notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO 2 sequestration.

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“…The exciting photon beam was achieved from the SX-700 monochromator attached to the storage ring ASTRID in Aarhus, Denmark [13][14][15]. The pressure of the residual gases in the experimental chamber during measurements did not exceed 1.33 x 10 -8 Pa.…”

Section: Methodsmentioning

confidence: 99%

Photoemission Study of Co Adsorbed on K/Cu(110). Analysis of Adsorbate Induced Structures

Godowski

Onsgaard²,

Christensen

et al. 1996

Acta Phys. Pol. A

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Improved adsorption characteristics of a K predosed Cu(110) surface with a coverage corresponding to a point before the work function minimum have been confirmed. Analysis of the CO-induced orbitals in the photoelectron spectra of the CO/K/Cu(110) interface for low coverages of carbon monoxide adsorbed at 118 K has been done. Noticeable changes of the parameters of the orbitals with increasing CO coverage have been registered. Elongation of the C-O bond without dissociation of the molecule has been deduced from the energetic separation of 3.4 eV between the 4σ and the 1π orbital. A weakening of the CO-interface bond with coverage has been found on the base of decreasing 5σ-1π separation with increasing 4σ/5σ intensity ratio. Perpendicular orientation of CO molecules to the plane of the substrate surface has been concluded from analysis of the constant initial state spectra of the 4σ and 5σ/1π orbitals.

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The interaction of CO2 with potassium-promoted Cu(100): adsorption, reactions and radiation induced dissociation of CO2

Cited by 25 publications

References 40 publications

On the origin of the elusive first intermediate of CO ₂ electroreduction

On the origin of the elusive first intermediate of CO ₂ electroreduction

Surface chemistry of carbon dioxide revisited

Photoemission Study of Co Adsorbed on K/Cu(110). Analysis of Adsorbate Induced Structures

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The interaction of CO2 with potassium-promoted Cu(100): adsorption, reactions and radiation induced dissociation of CO2

Cited by 25 publications

References 40 publications

On the origin of the elusive first intermediate of CO 2 electroreduction

On the origin of the elusive first intermediate of CO 2 electroreduction

Surface chemistry of carbon dioxide revisited

Photoemission Study of Co Adsorbed on K/Cu(110). Analysis of Adsorbate Induced Structures

Contact Info

Product

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On the origin of the elusive first intermediate of CO ₂ electroreduction

On the origin of the elusive first intermediate of CO ₂ electroreduction