Characterization of fundamental catalytic properties of MoS2/WS2 nanotubes and nanoclusters for desulfurization catalysis - a surface temperature study

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The prior project consisted of two main project lines. First, characterization of novel nanomaterials for hydrodesulfurization (HDS) applications. Second, studying more traditional model systems for HDS such as vapor-deposited silica-supported Mo and MoSx clusters. In the first subproject, we studied WS2 and MoS2 fullerene-like nanoparticles as well as WS2 nanotubes. Thiophene (C4H4S) was used as the probe molecule. Interestingly, metallic and sulfur-like adsorption sites could be identified on the silica-supported fullerene-particles system. Similar structures are seen for the traditional system (vapor-deposited clusters). Thus, this may be a kinetics fingerprint feature of modern HDS model systems. In addition, kinetics data allowed ... continued below

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Burghaus, U. July 5, 2012.

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Description

The prior project consisted of two main project lines. First, characterization of novel nanomaterials for hydrodesulfurization (HDS) applications. Second, studying more traditional model systems for HDS such as vapor-deposited silica-supported Mo and MoSx clusters. In the first subproject, we studied WS2 and MoS2 fullerene-like nanoparticles as well as WS2 nanotubes. Thiophene (C4H4S) was used as the probe molecule. Interestingly, metallic and sulfur-like adsorption sites could be identified on the silica-supported fullerene-particles system. Similar structures are seen for the traditional system (vapor-deposited clusters). Thus, this may be a kinetics fingerprint feature of modern HDS model systems. In addition, kinetics data allowed characterization of the different adsorption sites for thiophene on and inside WS2 nanotube bundles. The latter is a unique feature of nanotubes that has not been reported before for any inorganic nanotube system; however, examples are known for carbon nanotubes, including prior work of the PI. Although HDS has been studied for decades, utilizing nanotubes as nanosized HDS reactors has never been tried before, as far as we know. This is of interest from a fundamental perspective. Unfortunately, the HDS activity of the nanocatalysts at ultra-high vacuum (UHV) conditions was close to the detection limit of our techniques. Therefore, we propose to run experiments at ambient pressure on related nanopowder samples as part of the renewal application utilizing a now-available GC (gas chromatograph) setup. In addition, Ni and Co doped nanocatalyts are proposed for study. These dopants will boost the catalytic activity. In the second subproject of the prior grant, we studied HDS-related chemistry on more traditional supported cluster catalysts. Mo clusters supported by physical vapor deposition (PVD) on silica have been characterized. Two reaction pathways are evident when adsorbing thiophene on Mo and MoSx clusters: molecular adsorption and dissociation. PVD Mo clusters turned out to be very reactive toward thiophene bond activation. Sulfur and carbon residuals form, which poison the catalyst and sulfide the Mo clusters. Sulfided silica-supported MoSx samples are not reactive toward thiophene bond activation. In addition to S and C deposits, H2, H2S, and small organic molecules were detected in the gas phase. Catalyst reactivation procedures, including O2 and atomic hydrogen treatments, have been tested. Cluster size effects have been seen: thiophene adsorbs molecularly with larger binding energies on smaller clusters. However, larger clusters have smaller activation energy for C4H4S bond activation than smaller clusters. The latter is consistent with early catalysis studies. Kinetics and dynamics parameters have been determined quantitatively. We spent a significant amount of time on upgrades of our equipment. A 2nd-hand refurbished X-ray photoelectron spectrometer (XPS) has been integrated into the existing molecular beam scattering system and is already operational (supported by the DoE supplemental grant available in October 2009). We also added a time of flight (TOF) system to the beam scattering apparatus and improved on the accessible impact energy range (new nozzle heater and gas mixing manifold) for the beam scattering experiments. In addition, a GC-based powder atmospheric flow reactor for studies on powder samples is now operational. Furthermore, a 2nd UHV kinetics system has been upgraded as well. In summary, mostly single crystal systems have so far been considered in basic science studies about HDS. Industrial catalysts, however, can be better approximated with the supported cluster systems that we studied in this project. Furthermore, an entirely new class of HDS systems, namely fullerene-like particles and inorganic nanotubes, has been included. Studying new materials and systems has the potential to impact science and technology. The systems investigated are closely related to energy and environmental-related surface science/catalysis. This prior project, conducted at NDSU by a small team, resulted in a total of 14 printed publications,1-5, 7-12, 14, 19, 20eight months before the end of the funding period. In addition, collaborators at national laboratories and abroad were part of the projects, as proposed. More specifically, projects about HDS on MoS2 and WS2 inorganic fullerene-like nanoparticles,1, 5 inorganic WS2 nanotubes,2 Mo and MoS2 vapor-deposited nanoclusters,3 modeling,19 reviews/book chapter,7, 11 and side projects8-10 have been conducted, as proposed, acknowledging solely (exception ref.7) funding from this grant. A list of publications and coworkers is given in sect. 6.

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335 kB

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  • Report No.: DE-FG02-08ER15987-Final-Report
  • Grant Number: FG02-08ER15987
  • DOI: 10.2172/1045023 | External Link
  • Office of Scientific & Technical Information Report Number: 1045023
  • Archival Resource Key: ark:/67531/metadc842500

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  • July 5, 2012

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  • May 19, 2016, 9:45 a.m.

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  • June 20, 2016, 1:18 p.m.

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Burghaus, U. Characterization of fundamental catalytic properties of MoS2/WS2 nanotubes and nanoclusters for desulfurization catalysis - a surface temperature study, report, July 5, 2012; United States. (digital.library.unt.edu/ark:/67531/metadc842500/: accessed September 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.