Surface-level mechanistic studies of adsorbate–adsorbate interactions in heterogeneous catalysis by metals

The surface reactivity of furan, furfural, and furfuryl alcohol on oxygenprecovered Pd(111) (O/Pd (111)) was studied via temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) to understand the oxidation processes of more complex alcohols and aldehydes. The primary reaction pathway explored was furfuryl alcohol dehydrogenation to furfural, followed by decarbonylation to furan and subsequent ring opening of furan through O−C α scission; however, furfuryl alcohol and furfural also underwent other parallel reactions. At high coverages, deoxygenation of furfuryl alcohol to methylfuran was observed simultaneously with furfural production near 320 K, possibly through a disproportionation reaction of two alcohol adsorbates. Observation of furfural as a reaction product at this temperature was related to an increased prevalence of a weakly bound η 1 (O) aldehyde state near 250 K on O/Pd(111) as compared to clean Pd(111). Furfural also reacted with surface O to produce furoate (C 4 H 3 OCOO−), which primarily underwent decarboxylation to furan and CO 2 . The presence of surface oxygen resulted in a new, higher-temperature desorption channel for furan at 340 K; this channel was accompanied by the desorption of partial oxidation products 2(5H)-furanone and maleic anhydride. TPD experiments on 18 O/Pd(111) showed incorporation of surface oxygen into furfural, H 2 O, CO 2 , CO, 2(5H)-furanone, and maleic anhydride products, with the isotopic distributions suggesting that partial oxidation of furan occurred partly through a ringopened carboxylate.

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“…This suggests the importance of detailed investigations of interactions between adsorbates. 8,60 ■ CONCLUSIONS…”

Section: ■ Discussionmentioning

confidence: 99%

Ring-Opening and Oxidation Pathways of Furanic Oxygenates on Oxygen-Precovered Pd(111)

2014

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“…The presence of spectator species on the catalyst surface can enhance or poison electrocatalyst activity, as have been studied theoretically and experimentally [23][24][25][26][27] .…”

Section: Introductionmentioning

confidence: 99%

Role of CO* as a Spectator in CO₂ Electroreduction on RuO₂

2017

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“…adsorbate diffusion between the support and the particle, can have a significant contribution to the overall activity that surpasses the sum of the individual parts. 23 While all this calls for a simultaneous modeling of the catalyst particle and the support (especially for smaller nanometerscale particles), support effects are at present completely neglected in the vast majority of computational studies. Models that gradually start to integrate support effects rely typically either on fully periodic film formulations, in which several layers of the active phase are deposited on a periodically modeled support, 24 or on approaches in which finite clusters are deposited on a periodically modeled support.…”

Section: Introductionmentioning

confidence: 99%

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

Sabbe

Reyniers

Reuter

2012

Catal. Sci. Technol.

156

153

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Electronic structure calculations have emerged as a key contributor in modern heterogeneous catalysis research, though their application in chemical reaction engineering remains largely limited to academia. This perspective aims at encouraging the judicious use of first-principles kinetic models in industrial settings based on a critical discussion of present-day best practices, identifying existing gaps, and defining where further progress is needed.

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Surface-level mechanistic studies of adsorbate–adsorbate interactions in heterogeneous catalysis by metals

Cited by 50 publications

References 192 publications

Ring-Opening and Oxidation Pathways of Furanic Oxygenates on Oxygen-Precovered Pd(111)

Ring-Opening and Oxidation Pathways of Furanic Oxygenates on Oxygen-Precovered Pd(111)

Role of CO* as a Spectator in CO₂ Electroreduction on RuO₂

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

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Surface-level mechanistic studies of adsorbate–adsorbate interactions in heterogeneous catalysis by metals

Cited by 50 publications

References 192 publications

Ring-Opening and Oxidation Pathways of Furanic Oxygenates on Oxygen-Precovered Pd(111)

Ring-Opening and Oxidation Pathways of Furanic Oxygenates on Oxygen-Precovered Pd(111)

Role of CO* as a Spectator in CO2 Electroreduction on RuO2

First-principles kinetic modeling in heterogeneous catalysis: an industrial perspective on best-practice, gaps and needs

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Role of CO* as a Spectator in CO₂ Electroreduction on RuO₂