FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W3111904228> ?p ?o ?g. }

• W3111904228 endingPage "119797" @default.
• W3111904228 startingPage "119797" @default.
• W3111904228 abstract "Thiophene-H2 reactions proceed via sulfur removal and hydrogenation routes on dispersed metal nanoparticles that become decorated by refractory S adlayers during catalysis. The identity and kinetic relevance of the required elementary steps are described here based on rates measured at S-chemical potentials set by H2S/H2 ratios similar to those prevalent during practical catalysis on Re, ReSx, Ru, and Pt catalysts. The free energies of formation of S adatoms from H2S/H2 reactants are large and negative at low coverages (< −50 kJ mol−1 on Pt(111) and < −150 kJ mol−1 on Re(0001) and Ru(0001)), but strong repulsion among adatoms prevents full saturation, leading to sub-monolayer coverages and to passivated surfaces that expose uncovered interstices. The residual interstitial spaces (*) within adlayers of unreactive S-atoms (S′) bind intermediates and transition states reversibly, thus allowing these passivated surfaces to carry out catalytic turnovers. These interstices are larger on Pt than on Ru or Re surfaces, leading to concomitantly higher turnover rates for thiophene hydrogenation and desulfurization routes. The identity and kinetic relevance of elementary steps for desulfurization (to form C4 hydrocarbons) and hydrogenation (to form tetrahydrothiophene; THT) are similar among these catalysts; they involve kinetically-relevant H-addition steps of thiophene-derived intermediates that cleave their CS bonds or “over-hydrogenate” to THT in one surface sojourn. THT undergoes CS bond cleavage in secondary reactions that correct this over-hydrogenation to form the more unsaturated species that cleave CS bonds. THT/C4 product ratios are insensitive to H2S/H2 ratios and thiophene pressure, even though active interstitial spaces are covered by kinetically-detectable S* and bound thiophene; therefore, primary and secondary reactions must occur on the same active ensembles. The observed increase in THT/C4 ratios with H2 pressure shows that THT formation transition states involve a larger number of H-atoms than for CS cleavage. CS bonds cleave in species with partial unsaturation (H-contents between those in THT and thiophene), in processes that are reminiscent of the requirement to add or remove H-atoms from C and O atoms in cleaving CC and CO bonds in alkanes and alkanols, as well as CO bonds in CO hydrogenation reactions. The rate and selectivity data and the mechanistic conclusions described here show that thiophene hydrogenation and desulfurization routes require similar binding interstices within refractory S adlayers and that metal-sulfur bond energies act as indirect descriptors of reactivity because they determine the number, size, and binding properties of the exposed weakly-binding ensembles that stabilize the relevant transition states and enable catalytic turnovers." @default.
• W3111904228 created "2020-12-21" @default.
• W3111904228 creator A5002779860 @default.
• W3111904228 creator A5007609858 @default.
• W3111904228 creator A5052650376 @default.
• W3111904228 creator A5086150545 @default.
• W3111904228 date "2021-08-01" @default.
• W3111904228 modified "2023-10-01" @default.
• W3111904228 title "Hydrogenation and C S bond activation pathways in thiophene and tetrahydrothiophene reactions on sulfur-passivated surfaces of Ru, Pt, and Re nanoparticles" @default.
• W3111904228 cites W1965549692 @default.
• W3111904228 cites W1970127494 @default.
• W3111904228 cites W1979544533 @default.
• W3111904228 cites W1981368803 @default.
• W3111904228 cites W1989421746 @default.
• W3111904228 cites W1991149034 @default.
• W3111904228 cites W1996827346 @default.
• W3111904228 cites W1997009432 @default.
• W3111904228 cites W2007395042 @default.
• W3111904228 cites W2007405920 @default.
• W3111904228 cites W2012136032 @default.
• W3111904228 cites W2019601782 @default.
• W3111904228 cites W2019864083 @default.
• W3111904228 cites W2024908970 @default.
• W3111904228 cites W2025088735 @default.
• W3111904228 cites W2031243565 @default.
• W3111904228 cites W2036925363 @default.
• W3111904228 cites W2038489341 @default.
• W3111904228 cites W2047524879 @default.
• W3111904228 cites W2059605748 @default.
• W3111904228 cites W2063051042 @default.
• W3111904228 cites W2069061312 @default.
• W3111904228 cites W2071857745 @default.
• W3111904228 cites W2079105963 @default.
• W3111904228 cites W2081158181 @default.
• W3111904228 cites W2083222334 @default.
• W3111904228 cites W2085208616 @default.
• W3111904228 cites W2087698390 @default.
• W3111904228 cites W2092114982 @default.
• W3111904228 cites W2119316091 @default.
• W3111904228 cites W2120951899 @default.
• W3111904228 cites W2121396653 @default.
• W3111904228 cites W2144796577 @default.
• W3111904228 cites W2145179439 @default.
• W3111904228 cites W2148181703 @default.
• W3111904228 cites W2158781849 @default.
• W3111904228 cites W2171448977 @default.
• W3111904228 cites W2284403645 @default.
• W3111904228 cites W2316797751 @default.
• W3111904228 cites W2327480778 @default.
• W3111904228 cites W2418826892 @default.
• W3111904228 cites W2791351477 @default.
• W3111904228 cites W2806216134 @default.
• W3111904228 cites W2809289430 @default.
• W3111904228 cites W2913698403 @default.
• W3111904228 cites W2950510457 @default.
• W3111904228 cites W2951911311 @default.
• W3111904228 cites W3032299441 @default.
• W3111904228 cites W4254987721 @default.
• W3111904228 cites W57238465 @default.
• W3111904228 cites W4246369462 @default.
• W3111904228 doi "https://doi.org/10.1016/j.apcatb.2020.119797" @default.
• W3111904228 hasPublicationYear "2021" @default.
• W3111904228 type Work @default.
• W3111904228 sameAs 3111904228 @default.
• W3111904228 citedByCount "7" @default.
• W3111904228 countsByYear W31119042282021 @default.
• W3111904228 countsByYear W31119042282022 @default.
• W3111904228 countsByYear W31119042282023 @default.
• W3111904228 crossrefType "journal-article" @default.
• W3111904228 hasAuthorship W3111904228A5002779860 @default.
• W3111904228 hasAuthorship W3111904228A5007609858 @default.
• W3111904228 hasAuthorship W3111904228A5052650376 @default.
• W3111904228 hasAuthorship W3111904228A5086150545 @default.
• W3111904228 hasBestOaLocation W31119042281 @default.
• W3111904228 hasConcept C106773901 @default.
• W3111904228 hasConcept C161790260 @default.
• W3111904228 hasConcept C178790620 @default.
• W3111904228 hasConcept C179104552 @default.
• W3111904228 hasConcept C185592680 @default.
• W3111904228 hasConcept C2779953032 @default.
• W3111904228 hasConcept C2780477052 @default.
• W3111904228 hasConcept C3044715 @default.
• W3111904228 hasConcept C71240020 @default.
• W3111904228 hasConcept C75473681 @default.
• W3111904228 hasConceptScore W3111904228C106773901 @default.
• W3111904228 hasConceptScore W3111904228C161790260 @default.
• W3111904228 hasConceptScore W3111904228C178790620 @default.
• W3111904228 hasConceptScore W3111904228C179104552 @default.
• W3111904228 hasConceptScore W3111904228C185592680 @default.
• W3111904228 hasConceptScore W3111904228C2779953032 @default.
• W3111904228 hasConceptScore W3111904228C2780477052 @default.
• W3111904228 hasConceptScore W3111904228C3044715 @default.
• W3111904228 hasConceptScore W3111904228C71240020 @default.
• W3111904228 hasConceptScore W3111904228C75473681 @default.
• W3111904228 hasFunder F4320306084 @default.
• W3111904228 hasFunder F4320337480 @default.
• W3111904228 hasLocation W31119042281 @default.
• W3111904228 hasLocation W31119042282 @default.

• next