Catalytic Consequences of the Thermodynamic Activities at Metal Cluster Surfaces and Their Periodic Reactivity Trend for Methanol Oxidation

2014 ◽  
Vol 126 (45) ◽  
pp. 12344-12348 ◽  
Author(s):  
Weifeng Tu ◽  
Ya-Huei Cathy Chin
Author(s):  
L. T. Germinario

Understanding the role of metal cluster composition in determining catalytic selectivity and activity is of major interest in heterogeneous catalysis. The electron microscope is well established as a powerful tool for ultrastructural and compositional characterization of support and catalyst. Because the spatial resolution of x-ray microanalysis is defined by the smallest beam diameter into which the required number of electrons can be focused, the dedicated STEM with FEG is the instrument of choice. The main sources of errors in energy dispersive x-ray analysis (EDS) are: (1) beam-induced changes in specimen composition, (2) specimen drift, (3) instrumental factors which produce background radiation, and (4) basic statistical limitations which result in the detection of a finite number of x-ray photons. Digital beam techniques have been described for supported single-element metal clusters with spatial resolutions of about 10 nm. However, the detection of spurious characteristic x-rays away from catalyst particles produced images requiring several image processing steps.


Author(s):  
Richard D. Powell ◽  
James F. Hainfeld ◽  
Carol M. R. Halsey ◽  
David L. Spector ◽  
Shelley Kaurin ◽  
...  

Two new types of covalently linked, site-specific immunoprobes have been prepared using metal cluster labels, and used to stain components of cells. Combined fluorescein and 1.4 nm “Nanogold” labels were prepared by using the fluorescein-conjugated tris (aryl) phosphine ligand and the amino-substituted ligand in the synthesis of the Nanogold cluster. This cluster label was activated by reaction with a 60-fold excess of (sulfo-Succinimidyl-4-N-maleiniido-cyclohexane-l-carboxylate (sulfo-SMCC) at pH 7.5, separated from excess cross-linking reagent by gel filtration, and mixed in ten-fold excess with Goat Fab’ fragments against mouse IgG (obtained by reduction of F(ab’)2 fragments with 50 mM mercaptoethylamine hydrochloride). Labeled Fab’ fragments were isolated by gel filtration HPLC (Superose-12, Pharmacia). A combined Nanogold and Texas Red label was also prepared, using a Nanogold cluster derivatized with both and its protected analog: the cluster was reacted with an eight-fold excess of Texas Red sulfonyl chloride at pH 9.0, separated from excess Texas Red by gel filtration, then deprotected with HC1 in methanol to yield the amino-substituted label.


2010 ◽  
Vol 25 (4) ◽  
pp. 359-364 ◽  
Author(s):  
Xin ZENG ◽  
Xian-Xia YUAN ◽  
Xiao-Yun XIA ◽  
Juan DU ◽  
Hui-Juan ZHANG ◽  
...  

1992 ◽  
Vol 57 (12) ◽  
pp. 2529-2538 ◽  
Author(s):  
Krasimir Ivanov ◽  
Penka Litcheva ◽  
Dimitar Klissurski

Mn-Mo-O catalysts with a different Mo/Mn ratio have been prepared by precipitation. The precipitate composition as a function of solution concentration and pH was studied by X-ray, IR, thermal and chemical methods. Formation of manganese molybdates with MnMoO4.1.5H2O, Mn3Mo3O12.2.5H2O, and Mn3Mo4O15.4H2O composition has been supposed. It is concluded that pure MnMoO4 may be obtained in both acid and alkaline media, the pH values depending on the concentration of the initial solutions. The maximum Mo/Mn ratio in the precipitates is 1.33. The formation of pure Mn3Mo4O15.4H2O is possible in weakly acidic media. This process is favoured by increasing the concentration of initial solutions.


2001 ◽  
Vol 7 (S2) ◽  
pp. 1112-1113
Author(s):  
Rhonda M. Stroud ◽  
Jeffrey W. Long ◽  
Karen E. Swider-Lyons ◽  
Debra R. Rolison

To address how the chemical and structural heterogeneity of Pt50Ru50 nanoparticles affects methanol oxidation activity, we have employed an arsenal of transmission electron microscopy techniques (conventional bright field-imaging, selected area diffraction, atomic-resolution lattice imaging, electron-energy loss spectroscopy, and energy-dispersive x-ray spectroscopy) to characterize 2.5-nm particles in differing oxidation and hydration states. Our studies demonstrate that electrocatalysts containing a high fraction of Ru-rich hydrous oxide, as apposed to the anhydrous PtRu bimetallic alloy, have as much as 250x higher methanol oxidation activityThe nominally 2.5-nm Pt50Ru50 particles were studied in as-received, reduced and reoxidized forms. The reducing treatment consisted of 2 h at 100 °C in flowing 10% PL/argon mixture. For re-oxidation, the reduced particles were heated for 20 h at 100 °C in an H2O-saturated oxygen atmosphere. The particles were suspended in methanol, and pipetted onto holey-carboncoated Cu grids for TEM studies.


1968 ◽  
Vol 7 (1) ◽  
pp. 108-111 ◽  
Author(s):  
John M. Longo ◽  
Arthur W. Sleight

1986 ◽  
Vol 85 (2) ◽  
pp. 1198-1199 ◽  
Author(s):  
M. R. Zakin ◽  
R. O. Brickman ◽  
D. M. Cox ◽  
K. C. Reichmann ◽  
D. J. Trevor ◽  
...  

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