Loredana De Rogatis

Embedded Phases: A Way to Active and Stable Catalysts

Industrial catalysts are typically made of nanosized metal particles, carried by a solid support. The extremely small size of the particles maximizes the surface area exposed to the reactant, leading to higher reactivity. Moreover, the higher the number of metal atoms in contact with the support, the better the catalyst performance. In addition, peculiar properties have been observed for some metal/metal oxide particles of critical sizes. However, thermal stability of these nanostructures is limited by their size; smaller the particle size, the lower the thermal stability. The ability to fabricate and control the structure of nanoparticles allows to influence the resulting properties and, ultimately, to design stable catalysts with the desired characteristics. Tuning particle sizes provides the possibility to modulate the catalytic activity. Unique and unexpected properties have been observed by confining/embedding metal nanoparticles in inorganic channels or cavities, which indeed offers new opportunities for the design of advanced catalytic systems. Innovation in catalyst design is a powerful tool in realizing the goals of more green, efficient and sustainable industrial processes. The present Review focuses on the catalytic performance of noble metal- and non precious metal-based embedded catalysts with respect to traditional impregnated systems. Emphasis is dedicated to the improved thermal stability of these nanostructures compared to conventional systems.

Carbon Dioxide Hydrogenation on Ni(110)

We demonstrate that the key step for the reaction of CO 2 with hydrogen on Ni(110) is a change of the activated molecule coordination to the metal surface. At 90 K, CO 2 is negatively charged and chemically bonded via the carbon atom. When the temperature is increased and H approaches, the H-CO 2 complex flips and binds to the surface through the two oxygen atoms, while H binds to the carbon atom, thus yielding formate. We provide the atomic-level description of this process by means of conventional ultrahigh vacuum surface science techniques combined with density functional theory calculations and corroborated by high pressure reactivity tests. Knowledge about the details of the mechanisms involved in this reaction can yield a deeper comprehension of heterogeneous catalytic organic synthesis processes involving carbon dioxide as a reactant. We show why on Ni the CO 2 hydrogenation barrier is remarkably smaller than that on the common Cu metal-based catalyst. Our results provide a possible interpretation of the observed high catalytic activity of NiCu alloys.

Identification of the Structural Phases of CexZr1−xO2 by Eu(III) Luminescence Studies

Despite the wide application of ceria-zirconia based materials in Three Way Catalysts (TWCs), Solid Oxides Fuel Cells (SOFCs), and H(2) production and purification reactions, an active debate is still open on the correlation between their structure and redox/catalytic performances. Existing reports support the need of either (i) a homogeneous solid solution or (ii) materials with nanoscale heterogeneity to obtain high activity and stability. Here we report on a simple and inexpensive approach to solve this problem taking advantage of the luminescence properties of Eu(III), used as a structural probe introduced either in the bulk or on the surface of the samples. In this way, the real structure of ceria-zirconia materials can be revealed even for amorphous high surface area samples. Formation of small domains is observed in catalytically important metastable samples which appear homogeneous by conventional XRD.

NixCuy/Al2O3 based catalysts for hydrogen production

Ni(x wt.%)Cu(y wt.%)/Al2O3 samples were investigated as active and thermally stable catalysts for methanol and ethanol steam reforming. XRD data clearly evidenced the formation of a NiCu alloy under the adopted preparation procedure. The bimetallic systems exhibited improved activity in the methanol steam reforming with respect to the monometallic ones. The introduction of copper in the catalyst formulation showed a positive effect inhibiting the formation of methane, an undesirable by-product. On the other hand, in the ethanol steam reforming, the catalytic performance was less promising. Furthermore, the Ni : Cu ratio did not seem to affect the product distribution. However, enhanced stability was observed in the two subsequent run-up experiments, indicating the positive role played by the bimetallic systems.

Charge Redistribution at the Embedded Rh-Alumina Interface

An X-ray photoelectron spectroscopy (XPS) study was performed on model systems of Rh nanoparticles embedded into Al2O3. One of the main tasks was the investigation of the possibility to distinguish the Rh particles embedded into alumina matrix with respect to those on the surface of the support by means of their different electronic properties. A new component in the XPS spectra was found in the embedded sample after H2 treatment at 750 °C for 2 h. On the basis of these results and of other data, obtained by means of X-ray diffraction, temperature programmed reduction, N2 physisorption, and H2 chemisorption experiments, we suggest that this particular feature is associated with the encapsulation process of the metal nanoparticles rather than to the particle size effect. The anomalous charge redistribution of the embedded metallic clusters detected in the XPS measurements may be therefore used as a spectroscopic fingerprint of the embedding of Rh nanoparticles in Al2O3.