Transmission electron microscopy catalysts

Occasionally, especially in the developmental phase of catalyst research, it is necessary to determine the oxidation state, exact location, and dispersion of various elements in the catalyst. Eor these studies, either transmission electron microscopy (TEM) or scanning electron microscopy (SEM) combined with various high vacuum x-ray, electron, and ion spectroscopies are used routinely. 

Regarding a historical perspective on carbon nanotubes, very small diameter (less than 10 nm) carbon filaments were observed in the 1970 s through synthesis of vapor grown carbon fibers prepared by the decomposition of benzene at 1100°C in the presence of Fe catalyst particles of 10 nm diameter [11, 12]. However, no detailed systematic studies of such very thin filaments were reported in these early years, and it was not until lijima s observation of carbon nanotubes by high resolution transmission electron microscopy (HRTEM) that the carbon nanotube field was seriously launched. A direct stimulus to the systematic study of carbon filaments of very small diameters came from the discovery of fullerenes by Kroto, Smalley, and coworkers [1], The realization that the terminations of the carbon nanotubes were fullerene-like caps or hemispheres explained why the smallest diameter carbon nanotube observed would be the same as the diameter of the Ceo molecule, though theoretical predictions suggest that nanotubes arc more stable than fullerenes of the same radius [13]. The lijima observation heralded the entry of many scientists into the field of carbon nanotubes, stimulated especially by the un-... 

MgO-supported model Mo—Pd catalysts have been prepared from the bimetallic cluster [Mo2Pd2 /z3-CO)2(/r-CO)4(PPh3)2() -C2H )2 (Fig. 70) and monometallic precursors. Each supported sample was treated in H2 at various temperatures to form metallic palladium, and characterized by chemisorption of H2, CO, and O2, transmission electron microscopy, TPD of adsorbed CO, and EXAFS. The data showed that the presence of molybdenum in the bimetallic precursor helped to maintain the palladium in a highly dispersed form. In contrast, the sample prepared from the monometallie precursors was characterized by larger palladium particles and by weaker Mo—Pd interactions. ... 

Determined by inductively coupled plasma-mass spectrometry of acid digested catalyst samples Calculated from X-ray diffraction peak broadening at (101) foranatase and (110) formtile TiOa Mean particle diameter measured from transmission electron microscopy pictures of gold catalysts... 

Thus, the interaction of the primary beam with the sample provides a wealth of information on morphology, crystallography and chemical composition. Using transmission electron microscopy to make a projection of the sample density is a routine way to study particle sizes in catalysts. 

Transmission electron microscopy is one of the techniques most often used for the characterization of catalysts. In general, detection of supported particles is possible, provided that there is sufficient contrast between particles and support - a limitation that may impede applications of TEM on well-dispersed supported oxides. The determination of particle sizes or of distributions therein is now a routine matter, although it rests on the assumption that the size of the imaged particle is truly proportional to the size of the actual particle and that the detection probability is the same for all particles, independent of their dimensions. 

However, in more recent times science has made rapid strides in this direction. It is now possible to use EXAFS in situ during a catalytic reaction to examine the average coordination of metal atoms in the small particles which often exist in precious metal catalysts [2]. High resolution transmission electron microscopy has evolved to the level of atomic resolution, but can only be used ex-situ, or in situ with moderate pressures when special cells are fitted [3]. 

Transition metal oxides, rare earth oxides and various metal complexes deposited on their surface are typical phases of DeNO catalysts that lead to redox properties. For each of these phases, complementary tools exist for a proper characterization of the metal coordination number, oxidation state or nuclearity. Among all the techniques such as EPR [80], UV-vis [81] and IR, Raman, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS) and NMR, recently reviewed [82] for their application in the study of supported molecular metal complexes, Raman and IR spectroscopies are the only ones we will focus on. The major advantages offered by these spectroscopic techniques are that (1) they can detect XRD inactive amorphous surface metal oxide phases as well as crystalline nanophases and (2) they are able to collect information under various environmental conditions [83], We will describe their contributions to the study of both the support (oxide) and the deposited phase (metal complex). 

The structure of the catalysts was characterized by X-ray diffraction, IR-spectroscopy and transmission electron microscopy, their thermal stability was followed by thermal analytical method. The specific surface area and pore size distribution of the samples were determined by nitrogen adsorption isotherms. 

Chemical fixation for transmission electron microscopy prepares cells for the preservation of damage due to subsequent washing with aqueous solvents, dehydration with organic solvents such as ethanol or acetone, embedding in plastic resins, polymerization of the resins by heat, exothermic catalysts, or ultraviolet radiation, and imaging with high-energy electron beams in an electron microscope. 

But darkfield conventional transmission electron microscopy can now reveal monatomic steps directly, as the micrograph in Fig. 12 shows (71). Using this kind of approach it should be possible to ascertain quantitatively the extent of the interaction between a catalyst and its underlying support. 

Ffirai and Toshima have published several reports on the synthesis of transition-metal nanoparticles by alcoholic reduction of metal salts in the presence of a polymer such as polyvinylalcohol (PVA) or polyvinylpyrrolidone (PVP). This simple and reproducible process can be applied for the preparation of monometallic [32, 33] or bimetallic [34—39] nanoparticles. In this series of articles, the nanoparticles are characterized by different techniques such as transmission electronic microscopy (TEM), UV-visible spectroscopy, electron diffraction (EDX), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) or extended X-ray absorption fine structure (EXAFS, bimetallic systems). The great majority of the particles have a uniform size between 1 and 3 nm. These nanomaterials are efficient catalysts for olefin or diene hydrogenation under mild conditions (30°C, Ph2 = 1 bar)- In the case of bimetallic catalysts, the catalytic activity was seen to depend on their metal composition, and this may also have an influence on the selectivity of the partial hydrogenation of dienes. 

The forty-eighth volume of Advances in Catalysis includes a description of a new and increasingly well understood class of catalysts (titanosilicates), a review of transmission electron microscopy and related methods applied to catalyst characterization, and summaries of the chemistry and processes of isobutane-alkene alkylation and partial oxidation and C02 reforming of methane to synthesis gas. 

XI. Energy Filtered Transmission Electron Microscopy and Elemental Maps of Solid Catalysts Using EFTEM... 

Figure 9.7 Transmission electron microscopy of rhodium particles on a model titania support after reduction in H2 at 200 °C (top) and the same catalyst in the SMSI state after reduction at 500 °C (bottom). An amorphous overlayer on the surface of the SMSI catalyst is clearly discerned (from Logan etal. [25]).

Roth, C., Martz, N., and Fuess, H., Characterization of different Pt-Ru catalysts by x-ray diffraction and transmission electron microscopy, Phys. Chem. Chem. Phys., 3, 315,2001. 

The 11 nm-sized Ti02 were crystallized using either hydrothermal or thermal methods from 100 nm, amorphous gel spheres. The Ti02 crystal and agglomerate sizes were determined by X-ray diffraction (Philip 1080) and transmission electron microscopy (JEOL JEM 2010), respectively. The surface area and chemistry of the nanostructured Ti02 were analyzed by nitrogen physisorption (Coulter SA 3100) and Fourier transform infrared spectroscopy (FTIR, Perkin-Elmer GX 2000). Metal catalyst was deposited by incipient... 

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