Advanced catalysts and nanostructured materials: modern synthetic methods

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The continuous metallic framework has been generated by the sintering of adjacent Pd 0 clusters after the PVP removal. Dynamic TGA allowed to determine at which temperature the combustion starts i.

Daniel Miller

In fact, the presence of a very small amount of Pd catalyst affects the polymer thermal degradation both before and after ignition see Fig. Further, a residual weight loss of ca.

Two combustion stages are visible in the thermograms see Fig. This stage tends to become shorter with temperature increasing. These two stages are linked together through a short time interval in which the weight loss keeps almost constant. Such behavior can probably be ascribed to the time needed to saturate the Pd surface by molecular oxygen [ 9 ].

Pd catalyst is able to quantitatively convert the low-reactive molecular oxygen O 2 to a very reactive atomic oxygen species. The weight loss curve of pure PVP reaches its asymptotic value only after a very long time, and according to the applied regression analysis, it follows a second-order kinetic behavior. The constant A is the frequency factor, E a is the activation energy, and R is the gas constant.

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The Arrhenius plot ln k vs. The solid line is the linear fit of the experimental kinetic constants, and its slope depends on the activation energy E a. The calculated pre-exponential factor, A , was 1. For comparison, Fig. The calculated pre-exponential factor A was 7. According to Fig.

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The knowledge of the activation energy, E a , helps to develop hypothesis on the reaction mechanism. In fact, by comparing E a with the tabulated values of bond energies, one can determine which is the rate-limiting step in the combustion reaction under investigation. In fact, under fluxing oxygen condition constant oxygen concentration , the kinetic order of this elementary process is just like zero. The nanostructuration of the palladium phase plays an important role in this catalytic combustion process.

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The enhanced catalytic effect of nano-sized Pd compared to the micrometric Pd powder is visually evident. The catalytic activity of the nano-sized Pd increases; thanks to its high specific surface and enhanced catalytic site reactivity. As a consequence of such a kinetic mechanism atomic oxygen formation as a rate-limiting step , an effect of the nano-sized Pd catalyst on other polymer combustion could be expected too.

Therefore, nano-sized Pd catalyst could be industrially exploited in polymer incineration.

Biography Summary

In this paper, we have investigated the catalytic effect of palladium clusters in the PVP incineration reaction. We have found that the polymer incineration performed in presence of nano-sized Pd clusters is promoted by the oxygen atom action, which are more reactive than the molecular form.

After a short induction time, it was shown that the presence of nanoscopic Pd 0 catalyst determined an almost instantaneous combustion of the PVP. According to the kinetic analysis, a reaction mechanism involving the catalytic formation of atomic oxygen as a zero-order rate-limiting step has been proposed. Nano-sized Pd clusters have shown to exhibit a super-catalytic effect compared to micrometric Pd powder in the PVP incineration. This catalytic effect of nano-sized Pd could be of interest for the incineration of other polymers. LS contributed to the fabrication and to the characterization of the samples.

LS wrote part of the paper. GC and S De N participated to the development of the theoretical analysis and helped to draft the manuscript. All authors have read and approved the final manuscript. LS Dr. She received her degree in and her Ph. Her background is based on the knowledge of polymeric materials thermoplastic and thermosetting polymers , nanostructured materials, and different types of composites of the materials investigated.

GC Dr. His present research interests are in the field of advanced functional materials based on polymer-embedded inorganic nanostructures.


In particular, his activity concerns the development of new chemical routes for the controlled synthesis of metal and semiconductor clusters in polymeric matrices, the fabrication of devices based on properties of nanoscopic objects e. He has authored research articles published in international journals, 10 patents, and many conference papers. He is the editor of two Wiley books devoted to metal-polymer nanocomposites, and he is a member of the editorial board of different scientific journals.

His research interests include the development of quantum methodologies to the description of coherent phenomena in many body systems, quantum tomography, theoretical modeling for studying dynamical effects in mesoscopic systems, transport properties in nanostructured polymeric materials and biological media, and optical and electron beam propagation in nonlinear media and plasma.

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Science Headlines. The primary physical phenomena associated with ultrasound that are relevant to materials synthesis are cavitation and nebulization. Complementary to cavitational chemistry, the microdroplet reactors created by USP facilitate the formation of a wide range of nanocomposites. In this review, we summarize the fundamental principles of both synthetic methods and recent development in the applications of ultrasound in nanostructured materials synthesis.

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Advanced Materials Volume 22, Issue Kenneth S. Suslick Corresponding Author E-mail address: ksuslick illinois. Search for more papers by this author.