Catalytic hydrodesulfurization over the Mo(100) single crystal surface

Gellman, Andrew J.; Bussell, Mark E.; Somorjai, G.A.

doi:10.1016/0021-9517(87)90276-4

Cited by 65 publications

(16 citation statements)

References 21 publications

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“…A recent surface science study of thiophene HDS on partially sulfided molybdenum indicates that the rate-limiting step in desulfurization of this heterocycle occurs via C-S cleavage and is zero order in H2. 10 The formation of thiaferrole-like heterocycles is a plausible activation mechanism. Experimental Materials and Methods.…”

Section: Discussionmentioning

confidence: 99%

“…The desulfurization of thiophene adsorbed on molybdenum catalysts does not appear to involve hydrogen or surface sulfide. 10,11 Solution studies on the interactions of thiophenes with transition metals have been reported sporadically for the past 30 years. Thiophene is known to bind to metals in both an t?1-and ^-manner,12-22 and indications are that these binding modes are interrelated in the same way as the corresponding forms of the CBHB~ligand.14 Cationic complexes of t/5-thiophenes undergo addition reactions similar to those for cationic arene complexes,20 and very recent work has demonstrated this process labilizes the C-S bonds in compounds of the type [CpRu(t;5-RC4H4S)].…”

Section: Introductionmentioning

confidence: 99%

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Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Ogilvy¹,

Draganjac²,

Rauchfuss³

et al. 1988

Organometallics

125

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Ogilvy¹,

Draganjac²,

Rauchfuss³

et al. 1988

Organometallics

125

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“…Thiophene (C 4 H 4 S) has been used for many years as a model compound for the investigation of the hydrodesulfurization (HDS) process over single-crystal − and supported catalysts. , In addition to these catalytic studies, numerous surface science studies have been carried out in which spectroscopic techniques have been employed to characterize both the adsorption and reactions of thiophene on metal − and semiconductor − single-crystal surfaces. The surface chemistry of thiophene has also been examined on amorphous and single-crystalline molybdenum sulfide (MoS 2 ). , As might be expected, these substrates exhibit greatly different reactivities toward thiophene with early transition metal surfaces (e.g.…”

Section: Introductionmentioning

confidence: 99%

Infrared Spectroscopy and Temperature-Programmed Desorption Study of Adsorbed Thiophene on γ-Al₂O₃

et al. 1996

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The adsorption of thiophene (C4H4S) on γ-Al2O3 has been investigated in ultrahigh vacuum (UHV) using infrared (IR) spectroscopy and temperature-programmed desorption (TPD). Following thiophene adsorption onto γ-Al2O3 at 130 K, TPD reveals two peaks with maximum rates of desorption at 175 and ∼220 K. The former peak is assigned to desorption of multilayer thiophene while the latter peak is assigned to desorption of weakly chemisorbed thiophene from the alumina surface. IR spectroscopy of adsorbed thiophene at submonolayer coverages provides further evidence that thiophene interacts only weakly with the alumina support; no decomposition of the thiophene overlayer is observed upon heating to 600 K under UHV conditions or a partial pressure of thiophene of 3.0 Torr. Three kinds of adsorbed thiophene species exist on the alumina surface at saturation coverage: one in which thiophene interacts with hydroxyl groups, presumably via hydrogen bonding, a second in which thiophene is coordinated via its sulfur atom to coordinately unsaturated Al3+ sites on the surface, and a third species which is present only at high thiophene coverages. The heat of adsorption for thiophene on γ-Al2O3 has been determined under equilibrium conditions (P Th = 3.0 Torr) to be ΔH ads = −28.9 kJ/mol. A direct correlation has been established between the IR and TPD data, permitting integrated extinction coefficients to be determined for adsorbed thiophene in both the monolayer and multilayer coverage regimes. Extinction coefficients in the two coverage regimes are markedly different, underscoring the need to use care when interpreting the IR spectral intensities for adsorbed species. While, as expected, this study has shown that thiophene adsorbs only weakly on γ-Al2O3, more importantly it has shown that the combined IR−TPD methods can be used to determine both the thiophene coverage and the mode of bonding with the surface.

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“…Many early works used tritiated or 14 C labeled molecules such as [ 3 H] [ 14 C]ethylene or [ 14 C]carbon monoxide to monitor surface reactions in ultrahigh-vacuum conditions. Other studies used radioactive isotopes of sulfur and mercury to measure hydrodesulfurization and catalyst poisoning, respectively. , The use of noble gas atoms as radioactive probes has also been used in many experimental systems. Zhu et al prepared physiosorbed films of 37 Ar through vacuum deposition at cryogenic temperatures to measure the recoil energy of 37 Cl .…”

mentioning

confidence: 99%

“…Other studies used radioactive isotopes of sulfur and mercury to measure hydrodesulfurization and catalyst poisoning, respectively. 72,73 The use of noble gas atoms as radioactive probes has also been used in many experimental systems. Zhu et al prepared physiosorbed films of 37 Ar through vacuum deposition at cryogenic temperatures to measure the recoil energy of 37 Cl.…”

mentioning

confidence: 99%

Opportunities in the Synthesis and Design of Radioactive Thin Films and Nanoparticles

Coughlin

Mace

Sykes

2020

J. Phys. Chem. Lett.

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Studies of radioactive isotopes at the liquid−solid or gas−solid interface are enabling a detailed mechanistic understanding of the effects of radioactive decay on physical, biological, and chemical systems. In recent years, there has been a burgeoning interest in using radioactive isotopes for both imaging and therapeutic purposes by attaching them to the surface of colloidal nanoparticles. By merging the field of nanomedicine with the more mature field of internal radiation therapy, researchers are discovering new ways to diagnose and treat cancer. In this Perspective, we discuss state-of-the-art radioactive thin films as applied to both well-defined surfaces and more complex nanoparticles. We highlight the design considerations that are unique to radioactive films, which originate from the damaging and potentially self-destructive emissions produced during radioactive decay, and highlight future opportunities in the largely underexplored area between radioisotope chemistry and nanoscience.

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Catalytic hydrodesulfurization over the Mo(100) single crystal surface

Cited by 65 publications

References 21 publications

Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Infrared Spectroscopy and Temperature-Programmed Desorption Study of Adsorbed Thiophene on γ-Al₂O₃

Opportunities in the Synthesis and Design of Radioactive Thin Films and Nanoparticles

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Catalytic hydrodesulfurization over the Mo(100) single crystal surface

Cited by 65 publications

References 21 publications

Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Activation and desulfurization of thiophene and benzothiophene by iron carbonyls

Infrared Spectroscopy and Temperature-Programmed Desorption Study of Adsorbed Thiophene on γ-Al2O3

Opportunities in the Synthesis and Design of Radioactive Thin Films and Nanoparticles

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Infrared Spectroscopy and Temperature-Programmed Desorption Study of Adsorbed Thiophene on γ-Al₂O₃