Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

doi:10.1063/1.4882863

Cited by 27 publications

(62 citation statements)

References 64 publications

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“…This work provides insights for predicting water monomer and dimer diffusion behaviour on general surfaces, as well as guidance for future experiments of water dynamics on surfaces. Extending these findings, we think that the diffusion of other H-bonded clusters on surfaces 58,59 could display peculiar behaviours as a result of strong H-bond, diffusion mechanisms via H-bond rearrangements, and NQEs.…”

Section: Discussionsupporting

confidence: 59%

Origins of fast diffusion of water dimers on surfaces

et al. 2020

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The diffusion of water molecules and clusters across the surfaces of materials is important to a wide range of processes. Interestingly, experiments have shown that on certain substrates, water dimers can diffuse more rapidly than water monomers. Whilst explanations for anomalously fast diffusion have been presented for specific systems, the general underlying physical principles are not yet established. We investigate this through a systematic ab initio study of water monomer and dimer diffusion on a range of surfaces. Calculations reveal different mechanisms for fast water dimer diffusion, which is found to be more widespread than previously anticipated. The key factors affecting diffusion are the balance of water-water versus water-surface bonding and the ease with which hydrogen-bond exchange can occur (either through a classical over-the-barrier process or through quantum-mechanical tunnelling). We anticipate that the insights gained will be useful for understanding future experiments on the diffusion and clustering of hydrogen-bonded adsorbates.

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Section: Discussionsupporting

confidence: 59%

Origins of fast diffusion of water dimers on surfaces

et al. 2020

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“…Combining STM with TPD/R, we demonstrated that excess water is needed to convert methanol to formaldehyde on a Cu(111) surface. Since both water and methanol form hydrogen bonded clusters, the co-adsorption of methanol [44][45][46] and water [47,48] results in methanol-water networks that assist in the dehydrogenation of methanol to methoxy.…”

Section: Resultsmentioning

confidence: 99%

Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

et al. 2016

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The non oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 o C, and in ultra-high vacuum using model PtCu (111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are seven times higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a

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“…48,49 This vdW functional has been shown to perform extremely well in a wide range of molecular adsorption studies. [36][37][38][39] The plane-wave expansion was cut off at 550 eV and a Monkhorst-Pack k-points mesh of 4 x 4 x 1 was used for the slab systems.…”

Section: Methodsmentioning

confidence: 99%

Simulating Surfactant–Iron Oxide Interfaces: From Density Functional Theory to Molecular Dynamics

et al. 2019

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Understanding the behaviour of surfactant molecules on iron oxide surfaces is important for many industrial applications. Molecular dynamics (MD) simulations of such systems have been limited by the absence of a force-field (FF) which accurately describes the molecule-surface interactions. In this study, interaction energies from density functional theory (DFT) + U calculations with a van der Waals functional are used to parameterize a classical FF for MD simulations of amide surfactants on iron oxide surfaces. The Original FF, which was derived using mixing rules and surface Lennard-Jones (LJ) parameters developed for nonpolar molecules, were shown to significantly underestimate the adsorption energy and overestimate the equilibrium adsorption distance compared to DFT. Conversely, the Optimized FF showed excellent agreement with the interaction energies obtained from DFT calculations for a wide range of surface coverages and molecular conformations near to and adsorbed on α-Fe 2 O 3 (0001).

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Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

Cited by 27 publications

References 64 publications

Origins of fast diffusion of water dimers on surfaces

Origins of fast diffusion of water dimers on surfaces

Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

Simulating Surfactant–Iron Oxide Interfaces: From Density Functional Theory to Molecular Dynamics

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