Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

Hiebel, Fanny; Shong, Bonggeun; Chen, Wei; Madix, Robert J.; Kaxiras, Efthimios; Friend, Cynthia M.

doi:10.1038/ncomms13139

Cited by 23 publications

(42 citation statements)

References 59 publications

(70 reference statements)

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“…These findings support spectroscopic measurements which have shown that, independent of the crystal orientation, acetate anions prefer to bind to an Au surface in a bidentate configuration . They are also in agreement with DFT calculations and STM images acquired under UHV conditions for acetate adsorbed on Au(110) . It is not possible, however, from the spectroscopic data to distinguish between specific adsorption sites for the acetate adsorbate.…”

Section: Resultssupporting

confidence: 89%

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

et al. 2019

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The adsorption of acetate on an Au(111) electrode surface in contact with acetic acid at pH 2.7 was imaged in‐situ using scanning tunnelling microscopy (STM). Two different ordered structures were imaged for acetate adsorbed in the bidentate configuration on the unreconstructed ()1×1 surface at 0.95 V (vs. the saturated calomel electrode, SCE). The first structure,(19×19)R23.45∘ , is metastable and transforms at constant potential within 20 minutes to a (2×2) structure, which is thermodynamically more favourable. The (2×2) acetate adlayer starts to form at step edges and propagates via nucleation and growth onto terraces. The findings from in‐situ STM are in agreement with the electrochemical behaviour of acetate on Au(111) characterized by voltammetry. A comparison is made with formate adsorption on Au(111). While acetate is not reactive, in contrast to formate, it can act as a spectator species in formic acid electrooxidation.

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Section: Resultssupporting

confidence: 89%

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

et al. 2019

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“…The distance between the backbone of the species and the Cu surface increases when the vdW interactions were excluded, confirming the significant vdW effects on the structures. [26][27][28][29][30][31] The transition states for C-H bond breaking of 1-propoxy and 1-butoxy were reexamined with the updated adsorption structures. The NEB calculations suggested that the transition It is important to emphasize more generally the difficulty in finding the global minimum in the high-dimensional configuration space of adsorption for large molecules.…”

Section: Multiple Basins In the Energy Landscape Of Adsorptionmentioning

confidence: 99%

Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation

Chen¹,

Sun²,

Kozinsky³

et al. 2019

J. Phys. Chem. C

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If theory is to be able to predict the rates of catalytic reactions over extended ranges of temperature and pressure, it must provide accurate rate constants for elementary reaction steps, including both the activation energy and pre-exponential factor. A standing difficulty with this objective is the treatment of floppy modes in the partition function for the adsorbed species. This issue leads to limited accuracy in the pre-exponential factor computed for realistic systems. Here we investigate the C-H bond breaking for a series of linear-chain alkoxides on Cu(110) using density functional theory, since the results can be compared to experimental data for the rate constants. The structural similarity of these species enables us to understand the systematic effect of molecular size on the frustrated motions and pre-exponential factor. First, we discuss the complexities of finding the global minimum structure of the adsorbed species and highlight the high dimensionality of configuration space to be sampled. Then, we analyze the motions of harmonic normal modes, including the motions of the underlying metal atoms, and compute the harmonic pre-exponential factors. To account for periodic frustrated rotations we use the hindered rotor model: this motion significantly decreases the pre-exponential factor in the C-H bond breaking, the effect increasing with molecular size. We also estimate the anharmonic effect using the Morse treatment of potentials. The activation energy and pre-exponential factor computed for CH 3 O are in excellent quantitative agreement with experiment. The trends computed for the homologous series of alcohols are also reflected by experiment.

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“…Following CO 2 reduction to -CH 2 on the surface of Cu, dimerization of the latter with free CO from Ag would occur to give the C-C bond on the surface. Once formed on the surface, further reduction of acetaldehyde would give acetate as the final product (40).…”

Section: +mentioning

confidence: 99%

CO ₂ reduction to acetate in mixtures of ultrasmall (Cu) _n ,(Ag) _m bimetallic nanoparticles

Wang

Dares

et al. 2017

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

101

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Monodispersed mixtures of 6-nm Cu and Ag nanoparticles were prepared by electrochemical reduction on electrochemically polymerized -Fe(vbpy)(PF) film electrodes on glassy carbon. Conversion of the complex to -Fe(vbpy)(CN) followed by surface binding of salts of the cations and electrochemical reduction gave a mixture of chemically distinct clusters on the surface, (Cu) ,(Ag) |polymer|glassy carbon electrode (GCE), as shown by X-ray photoelectron spectroscopy (XPS) measurements. A (Cu),(Ag)|(80-monolayer--Fe(vbpy)|GCE electrode at -1.33 V vs. reversible hydrogen electrode (RHE) in 0.5 M KHCO, with 8 ppm added benzotriazole (BTA) at 0 °C, gave acetate with a faradaic efficiency of 21.2%.

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Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

Cited by 23 publications

References 59 publications

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation

CO ₂ reduction to acetate in mixtures of ultrasmall (Cu) _n ,(Ag) _m bimetallic nanoparticles

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Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

Cited by 23 publications

References 59 publications

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

Adsorption of Acetate on Au(111): An in‐situ Scanning Tunnelling Microscopy Study and Implications on Formic Acid Electrooxidation

Effect of Frustrated Rotations on the Pre-Exponential Factor for Unimolecular Reactions on Surfaces: A Case Study of Alkoxy Dehydrogenation

CO 2 reduction to acetate in mixtures of ultrasmall (Cu) n ,(Ag) m bimetallic nanoparticles

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CO ₂ reduction to acetate in mixtures of ultrasmall (Cu) _n ,(Ag) _m bimetallic nanoparticles