Spectroscopic investigation of Titania-supported gold nanoparticles prepared by a modified deposition/precipitation method for the oxidation of CO

The spectroscopic characterization of a material is a fundamental tool for understanding the structure–activity correlation for catalytic purposes. Regarding supported nanoparticles, this perspective has acquired more relevance in recent years and several techniques have been employed. In this work diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), coupled with CO adsorption, was used to investigate a modified deposition/precipitation method (DP-UC) for the preparation of supported gold nanoparticles with very low metal loading (0.1–0.5 wt %). This promising synthetic route involves the use of urea as basic agent and NaBH4 as chemical reductant in contrast to the traditional high-temperature reduction step. The systematic IR spectroscopic study of the Au loading was combined with CO oxidation catalytic tests. The evaluation of the results was also supported by several other techniques, such as X-ray photoelectron spectroscopy, N2 physisorption, and transmission electron microscopy. Particular attention was given to the evaluation of the gold electronic state, surface dispersion, particle size, and the corresponding structure–activity relationship

Low-temperature water-gas shift on Pt/Ce0.8La0.2O2−δ–CNT: The effect of Ce0.8La0.2O2−δ/CNT ratio

Hybrid materials of (100 − x) wt% Ce0.8La0.2O2−δ–x wt% CNT composition (x = 0, 7.5, 20.5, 32.5, 44.1 and 100) were synthesized using the urea-assisted co-precipitation method and used as supports of 0.5 wt% Pt toward the low-temperature WGS (LT-WGS) reaction. The main focus of this work was to provide fundamental understanding of the effect of Ce0.8La0.2O2−δ/CNT ratio on the LT-WGS catalytic activity of such materials. It was found that the material containing 44.1 wt% CNT presented the best catalytic activity (kinetic rate and CO conversion), result that is correlated with the following parameters: (i) Pt-CO bond strength (TPD-CO), (ii) extent of dispersion of the Ce0.8La0.2O2−δ phase in the hybrid support system and, thus of the Pt phase; the larger dispersion of the Ce0.8La0.2O2−δ phase had a direct impact on its reducibility ability (labile oxygen species), (iii) concentration of surface Ce3+ species (XPS), indication for an increased concentration of oxygen vacant sites, (iv) PtH bond strength (H2-TPD studies), and (v) concentration of active carbon-containing intermediates, “C-pool” formed around each Pt nanoparticle (SSITKA studies). WGS kinetic studies at 300 °C revealed that the reaction order with respect to CO was 0.17 and 0.13 for the catalysts containing 20.5 and 44.1 wt% CNT, respectively, while the reaction order with respect to H2O was 1.40 for the latter CNT loading. Oxidation of CNTs over the catalyst containing 44.1 wt% of CNTs occurred at temperatures larger than 400 °C, result of practical importance for the LT-WGS reaction. The proposed WGS reaction mechanism over the present catalytic materials is that of “redox” in parallel with the “associative with –OH group regeneration” mechanism.The European Regional Development Fund, the Republic of Cyprus and the Research Promotion Foundation of Cyprus are gratefully acknowledged for their financial support through the project TECHNOLOGY/0308(BE)/05.Peer Reviewe

Stability of nanoparticle production by atmospheric-pressure spark ablation

The stability of nanoparticle (NP) production by atmospheric-pressure spark ablation was studied and found to depend on the composition of the electrodes and the carrier gas (here N2 or Ar). For materials that do not react with N2, such as Pd and Ni, NP production was rather stable regardless of the carrier gas employed. In contrast, for materials that can easily produce nitride species (e.g., Al and Mg), both the concentration and size of the resulting NPs exhibited noticeable fluctuations, when ablating them in N2, which are more pronounced when the electrical energy input to the system is low. The variation in concentration and particle size is attributed to the formation of a metal-nitride region on the face of the electrodes where the sparks hit, as a result of its reaction with the carrier gas, altering the electrical and thermal conductivity, and consequently the ablatability of the electrode at that region. This explanation was corroborated by offline analysis of the face surface of the electrodes, showing two chemically distinct regions: one with high content of N and one without. In addition, the concentration of the Al and Mg NPs produced in N2 decreased gradually over time until it reached a plateau after several hours. When using Ar, the fluctuation and decreasing trend in NP production, and consequently the formation of nitride compounds on the face surface of the electrodes, were negligible, providing an effective solution for stable ablation of materials that can easily react with N2.ChemE/Materials for Energy Conversion and StorageAtmospheric Remote Sensin

H2-SCR of NOx on low-SSA CeO2-supported Pd: The effect of Pd particle size

The H2-SCR of NO was investigated in the 130−220 °C range over low-SSA CeO2-supported Pd of varying particle size, dPd (ca. 13−45 nm). Relationships were derived between dPd and the specific integral rate (per gram of Pd or length of metal-support interface), NO conversion, N2-selectivity, TOFNO and the concentration of active NOx-s. The large enhancement in the rate of NO conversion per gram of Pd metal over the small Pd particles was found to be largely related to the increase in the concentration of active NOx formed within a zone around the Pd-ceria interface and the rate of H-spillover. The effect of H2O on the integral rate and N2-selectvity as a function of dp (nm) was also investigated. © 2021 Elsevier B.V

Water-gas shift reaction on Pt/Ce1- xTixO 2-δ: The effect of Ce/Ti ratio

Pt nanoparticles (1.2–2.0 nm size) supported on Ce1–xTixO2−δ (x = 0, 0.2, 0.5, 0.8, and 1.0) carriers synthesized by the citrate sol–gel method were tested toward the water–gas shift (WGS) reaction in the 200–350 °C range. A deep insight into the effect of two structural parameters, the chemical composition of support (Ce/Ti atom ratio), and the Pt particle size on the catalytic performance of Pt-loaded catalysts was realized after employing in situ X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM) and HAADF/STEM, scanning electron microscopy (SEM), in situ Raman and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopies under different gas atmospheres, H2 temperature-programmed reduction (H2-TPR), and temperature-programmed desorption (NH3-TPD and CO2-TPD) techniques. The 0.5 wt % Pt/Ce0.8Ti0.2O2−δ solid (dPt = 1.7 nm) was found to be by far the best catalyst among all the other solids investigated. In particular, at 250 °C the CO conversion over Pt/Ce0.8Ti0.2O2−δ was increased by a factor of 2.5 and 1.9 compared to Pt/TiO2 and Pt/CeO2, respectively. The catalytic superiority of the Pt/Ce0.8Ti0.2O2−δ solid is the result of the support’s (i) robust morphology preserved during the WGS reaction, (ii) moderate acidity and basicity, and (iii) better reducibility at lower temperatures and the significant reduction of “coking” on the Pt surface and of carbonate accumulation on the Ce0.8Ti0.2O2−δ support. Several of these properties largely influenced the reactivity of sites (k, s–1) at the Pt–support interface. In particular, the specific WGS reaction rate at 200 °C expressed per length of the Pt–support interface (μmol CO cm–1 s–1) was found to be 2.2 and 4.6 times larger on Pt supported on Ce0.8Ti0.2O2−δ (Ti4+-doped CeO2) compared to TiO2 and CeO2 alone, respectively.The European Regional Development Fund, the Republic of Cyprus, the Research Promotion Foundation of Cyprus, and the Research Committee of the University of Cyprus are gratefully acknowledged for their financial support through the project TEXNO/0308(BE)/05. S.B. acknowledges financial support from the COST Action CM1104.Peer Reviewe

Controlling the optical properties of nanostructured oxide-based polymer films

International audienceA bulk scale process is implemented for the production of nanostructured film composites comprising unary or multi-component metal oxide nanoparticles dispersed in a suitable polymer matrix. The as-received nanoparticles, namely Al2O3, SiO2 and TiO2 and binary combinations, are treated following specific chemical and mechanical processes in order to be suspended at the optimal size and composition. Subsequently, a polymer extrusion technique is employed for the fabrication of each film, while the molten polymer is mixed with the treated metal oxide nanoparticles. Transmission and reflection measurements are performed in order to map the optical properties of the fabricated, nanostructured films in the UV, VIS and IR. The results substantiate the capability of the overall methodology to regulate the optical properties of the films depending on the type of nanoparticle formation which can be adjusted both in size and composition

Controlling the optical properties of nanostructured oxide-based polymer films

A bulk scale process is implemented for the production of nanostructured film composites comprising unary or multi-component metal oxide nanoparticles dispersed in a suitable polymer matrix. The as-received nanoparticles, namely Al[Formula: see text]O[Formula: see text], SiO[Formula: see text] and TiO[Formula: see text] and binary combinations, are treated following specific chemical and mechanical processes in order to be suspended at the optimal size and composition. Subsequently, a polymer extrusion technique is employed for the fabrication of each film, while the molten polymer is mixed with the treated metal oxide nanoparticles. Transmission and reflection measurements are performed in order to map the optical properties of the fabricated, nanostructured films in the UV, VIS and IR. The results substantiate the capability of the overall methodology to regulate the optical properties of the films depending on the type of nanoparticle formation which can be adjusted both in size and composition

Tuning atomic-scale mixing of nanoparticles produced by atmospheric-pressure spark ablation

Nanoparticles (NPs) mixed at the atomic scale have been synthesized by atmospheric-pressure spark ablation using pairs of Pd and Hf electrodes. Gravimetric analysis of the electrodes showed that the fraction of each material in the resulting mixed NPs can be varied from ca. 15-85 at% to 85-15 at% by employing different combinations of electrode polarities and thicknesses. These results were also qualitatively corroborated by microscopy and elemental analysis of the produced NPs. When using pairs of electrodes having the same diameter, the material from the one at negative polarity was represented at a substantially higher fraction in the mixed NPs regardless of whether a pair of thin or thick electrodes were employed. This can be attributed to the higher ablation rate of the electrodes at the negative polarity, as already known from earlier experiments. When using electrodes of different diameters, the fraction of the element from the thinner electrode was always higher. This is because thinner electrodes are ablated more effectively due to, at least in part, the increased importance of the associated heat losses compared to its thicker counterpart. In those cases, the polarity of the electrodes had a significantly smaller effect. Overall, our results demonstrate, for the first time, that spark ablation can be used to control atomic scale mixing and thus produce alloyed NPs with compositions that can be tuned to a good extent by simply using different combinations of electrode diameters and polarities. This expands the capabilities of the technique for producing mixed nanoparticle building blocks of well-defined composition that are highly desired for a wide range of applications.ChemE/Materials for Energy Conversion and StorageAtmospheric Remote Sensin