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This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other sig...

Support plays a complex role in catalysis by supported metal oxides and the exact support effect still remains elusive. One of the approaches to gain fundamental insights into the support effect is to utilize model support systems. In this study, we employed for the first time titania nanoshapes as the model supports and investigated how the variation of surface structure of the support (titania, TiO2) impacts the catalysis of supported oxide (vanadia, VOx). TiO2 truncated rhombi, spheres and rods were synthesized via hydrothermal method and characterized with XRD and TEM. These TiO2 nanoshapes represent different mixtures of surface facets including [1 0 1], [0 1 0] and [0 0 1] and were used to support vanadia. The structure of supported VOx species was characterized in detail with in situ Raman spectroscopy as a function of loading on the three TiO2 nanoshapes. Oxidative dehydrogenation (ODH) of isobutane to isobutene was used as a model reaction to test how the support shape influences the activity, selectivity and activation energy of the surface VOx species. It was shown that the shape of TiO2 support does not pose evident effect on either the structure of surface VOx species or the catalytic performance of surfacemore » VOx species in isobutane ODH reaction. Finally, this insignificant support shape effect was ascribed to the small difference in the surface oxygen vacancy formation energy among the different TiO2 surfaces and the multi-faceting nature of the TiO2 nanoshapes.« less

We investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. The results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.

In this study, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In particular, we investigated the interaction of hydrogen with lithium and sodium doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C 60 H 60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77 K to 303 K were measured demonstrating an increase in hydrogen uptake versus pure C 60 and increased isosteric heats of adsorption for the lithium doped fullerene Li 12 C 60 . The hydrogen uptake in Na 6 C 60 , Li 6 C 60 , and Li 12 C 60 was enhanced compared to pure C 60 . However, despite these improvements the low amount of physisorbed hydrogen at 1 atm and 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.

Fullerene-derived buckybowl fractions dispersed on mesoporous silica constitute an ideal model for studying the catalysis of graphitic forms of carbon since the dispersed carbon nanostructures contain a high ratio of edge defects and curvature induced by non-six-membered rings. Dispersion of the active centers on an easily accessible high surface area material allowed for high density of surface active sites associated with oxygenated structures. This report illustrates a facile method of creating model polycyclic aromatic nano-structures that are not only active for alkane C–H bond activation and oxidative dehydrogenation but also can be practical catalysts to be eventually used in industry.

We investigated the impact of ZrO 2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO 2 and SiO 2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO 2 surface area and improve sulfur tolerance, a Pd support with ZrO 2 -dispersed onto SiO 2 was studied. The physicochemical properties of the catalysts were examined using ICP, N 2 sorption, XRD, SEM, TEM, and NH 3 -, CO 2 -, and NO x -TPD. The activity of the Pd catalysts were measured from 60 to 600 °C in a flow of 4000 ppm CO, 500 ppm NO, 1000 ppm C 3 H 6 , 4% O 2 , 5% H 2 O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO 2 -containing catalysts showed considerably higher CO and C 3 H 6 oxidation activity than Pd/SiO 2 under the reaction conditions studied. The good performance of ZrO 2 -containing catalysts appeared to be due in part to high Pd dispersion resulting from strong Pd and support interaction. Another beneficial effect of strong interaction between Pd and ZrO 2 was manifested as a greater hydrothermal stability with good oxidation activity even after aging at 800 and 900 °C for 16 h. In contrast, Pd/SiO 2 suffered significant performance loss due to Pd particle coarsening. Although the Pd/ZrO 2 -SiO 2 catalyst was not more active than Pd/ZrO 2 , improved tolerance to sulfur was realized. Unlike the bulk ZrO 2 support, the ZrO 2 -incorporated SiO 2 presented only weak basicity leading to a superior sulfur tolerance of Pd/ZrO 2 -SiO 2 . These results confirmed the potential of developing Pd-based oxidation catalysts with enhanced low-temperature activity and durability using ZrO 2 -SiO 2 supports. Controlling morphology and accessible area of the dispersed ZrO 2 layer appeared critical to further maximize the catalytic performance.