Thanh-Son Nguyen

Ultrastable iridium–ceria nanopowders synthesized in one step by solution combustion for catalytic hydrogen production

Mesoporous ceria loaded with 0.06–0.93 wt% iridium was synthesized in one step by the ambient air combustion of an aqueous solution of ceric ammonium nitrate, ammonium hexachloroiridate, and glycine fuel. The structural properties of the powders, and the influence of such parameters as Ir loading and thermochemical post-treatments, were investigated combining aberration-corrected HRTEM, SEM, in situ XRD, XPS, DRIFTS, and Raman spectroscopy. The materials, which appeared spongy at the micrometer scale, exhibited ca. 30 nm-sized ceria crystallites with a layered structure at the nanoscale. After reducing treatments, Ir nanoparticles anchored at the surface of ceria grains were identified, and their size (ca. 2 nm) did not evolve upon further heating at up to 900 °C. A detailed picture of the Ir–CeO2 interface could be established, with the presence of Irx+–O2−–Ce3+ entities along with oxygen vacancies. The powders loaded with only 0.1 wt% Ir were successfully employed as catalysts for the production of hydrogen from methane and water in low-steam conditions at 750 °C. Due to their higher Ir dispersion and stronger Ir–CeO2 interaction, the combustion-synthesized materials outperformed their conventionally prepared counterparts in terms of activity and stability, making them promising as active catalytic layers for solid-oxide fuel cells integrating the gradual internal reforming concept.

Sensitivity of CO oxidation toward metal oxidation state in ceria-supported catalysts: an operando DRIFTS-MS study

The oxidation of carbon monoxide has been studied on pristine CeO2, Rh–CeO2, and Pt–CeO2 powders prepared in one step by solution combustion synthesis (SCS). The reaction was cycled between an oxygen-rich and a CO-rich feed with regard to the stoichiometric conditions. CO2 production was monitored by mass spectrometry, while the surface species were probed by operando DRIFTS (Diffuse Reflectance Infrared Fourier Transform Spectroscopy). Whereas the reaction starts above 150 °C on CeO2 and Rh–CeO2 and does not depend on the state of the surface (oxidized or reduced), the reaction on Pt–CeO2 shows strong dependency on the initial state and substantial activity is achieved at much lower temperatures with the CO-rich feed. We relate this result to the change in the oxidation state of Pt via strong interaction with ceria.

Monitoring in situ the colloidal synthesis of AuRh/TiO2 selective-hydrogenation nanocatalysts

AuRh nanoparticles (NPs) of various compositions and sizes in the 2–4 nm range were synthesized using a colloidal approach and were characterized at each preparation step by dynamic light scattering (DLS), ultraviolet-visible (UV-vis) spectroscopy, and liquid-phase transmission electron microscopy (liquid TEM). The AuRh colloids appear relatively instable, leading to their gradual coalescence. After fast immobilization of the metallic nanoparticles on rutile TiO2 nanorods, the materials were investigated by high-resolution transmission electron microscopy (HRTEM) and low-temperature CO adsorption monitored by Fourier transform infrared (FTIR) spectroscopy. The inherent lack of miscibility between Au and Rh leads to partial segregation inside the NPs, which is further exalted after a reducing thermal treatment applied for PVA removal. The catalytic properties in the liquid-phase selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde are strongly influenced by these nanostructural modifications. While in as-prepared samples the intermixing between Au and Rh phases promotes the catalytic performances for Rh-rich AuRh catalysts through Au-induced stabilization of Rh in its metallic form, segregation into Janus particles after reduction decreases the catalytic activity.

Uncovering the three-dimensional structure of combustion-synthesized noble metal-ceria nanocatalysts

With its unique redox properties, ceria is an oxide with a range of applications, including automotive catalytic converters, which consist of platinum‐group metal nanoparticles on ceria‐containing supports. In this work, the 3 D architecture of a ceria‐based material synthesized by the widely employed glycine‐nitrate solution combustion method is revealed for the first time. Together with N2 adsorption volumetry, scanning transmission electron microscopy (STEM) and scanning electron microscopy (SEM), STEM tomography provides a comprehensive picture of the multimodal porous network of a pre‐reduced Pt‐CeO2 catalyst, from the nanometer to the micrometer scale. This material consists of ceria nanocrystallites forming 3 D aggregates and puzzle‐like 2 D walls separating large roundish mesopores and macropores. The small voids between imperfectly assembled crystallites give rise to some microporosity. In addition, it is demonstrated that a significant proportion of platinum nanoparticles (3–4 nm) are not located at the ceria surface following the one‐step synthesis process, about half of them are buried within ceria. This result is valid for another metal (Rh) and another fuel (oxalyl dihydrazide), and has important implications for heterogeneous catalysis.