Engineering Multidefects on Cex Si1- x O2- δ Nanocomposites for the Catalytic Ozonation Reaction.

Herein, it is shown that by engineering defects on Cex Si1- x O2- δ nanocomposites synthesized via flame spray pyrolysis, oxygen vacancies can be created with an increased density of trapped electrons, enhancing the formation of reactive oxygen species (ROSs) and hydroxyl radicals in an ozone-filled environment. Spectroscopic analysis and density functional theory calculations indicate that two-electron oxygen vacancies (OV 0 ) or peroxide species, and their degree of clustering, play a critical role in forming reactive radicals. It is also found that a higher Si content in the binary oxide imposes a high OV 0 ratio and, consequently, higher catalytic activity. Si inclusion in the nanocomposite appears to stabilize the surface oxygen vacancies as well as increase the reactive electron density at these sites. A mechanistic study on effective ROSs generated during catalytic ozonation reveals that the hydroxyl radical is the most effective ROS for organic degradation and is formed primarily through H2 O2 generation in the presence of the OV 0 . Examining the binary oxides offers insights on the contribution of oxygen vacancies and their state of charge to catalytic reactions, in this instance for the catalytic ozonation of organic compounds.

Electronic Effects of Support Doping on Hydrotalcite-Supported Iridium N-Heterocyclic Carbene Complexes.

The electronic effects of supports on immobilized organometallic complexes impact their activity and lifetime, yet remain poorly understood. Here we describe a systematic study of the support effects experienced by an organometallic complex immobilized on doped hydrotalcite-like materials. To that end, we describe the synthesis and characterization of the first organometallic species immobilized on a palette of doped hydrotalcites via sulfonate linkers. The organometallic species consists of iridium N-heterocyclic carbene (NHC) carbonyl complex ([Na][Ir-(NHC-Ph-SO3)2(CO)2]), a highly active molecular catalyst for transfer hydrogenation of glycerol. The hydrotalcite supports are composed of Al, Mg, and a compatible transition-metal dopant (Fe, Cu, Ni, Zn). The materials were characterized extensively by STEM, XPS, TGA, PXRD, FT-IR, N2 desorption, ICP-AES, TPD, and microcalorimetry to probe the morphology and electronic properties of the support and elucidate structure-property relationships.

Plasma-Induced Catalyst Support Defects for the Photothermal Methanation of Carbon Dioxide.

The presence of defects in a catalyst support is known to benefit catalytic activity. In this work, a He-plasma treatment-based strategy for introducing and stabilising defects on a Ni/TiO2 catalyst for photothermal CO2 hydrogenation was established. The impact of pretreatment step sequence-which comprised He-plasma treatment and reduction/passivation-on defect generation and stabilisation within the support was evaluated. Characterisation of the Ni/TiO2 catalysts indicated that defects created in the TiO2 support during the initial plasma treatment stage were then stabilised by the reduction/passivation process, (P-R)Ni/TiO2. Conversely, performing reduction/passivation first, (R-P)Ni/TiO2, invoked a resistance to subsequent defect formation upon plasma treatment and consequently, poorer photothermal catalytic activity. The plasma treatment altered the metal-support interaction and ease of catalyst reduction. Under photothermal conditions, (P-R)Ni/TiO2 reached the highest methane production in 75 min, while (R-P)Ni/TiO2 required 165 min. Decoupling the impacts of light and heat indicated thermal dominance of the reaction with CO2 conversion observed from 200 °C onwards. Methane was the primary product with carbon monoxide detected at 350 °C (~2%) and 400 °C (~5%). Overall, the findings demonstrate the importance of pretreatment step sequence when utilising plasma treatment to generate active defect sites in a catalyst support.

Asymmetrical Double Flame Spray Pyrolysis-Designed SiO2/Ce0.7Zr0.3O2 for the Dry Reforming of Methane.

Silica has the potential to enhance the performance of ceria-zirconia as a support for the dry reforming of methane; however, controlling the integration of silica with the ceria-zirconia using flame spray pyrolysis (FSP) is a significant challenge. To address this challenge, an asymmetrically variable double-FSP (DFSP) system was established to control the SiO2 interaction with Ce0.7Zr0.3O2. The engineered materials were then utilized as supports for Ni for the dry reforming of methane. Initially, silica formation during FSP synthesis was examined where it was revealed that, at a low precursor concentration (<1.5 M tetraethyl orthosilicate in xylenes), the physical characteristics of the silica varied differently in relation to what is typically encountered during FSP synthesis. Explicitly, on using a 0.5 M tetraethyl orthosilicate precursor, increasing the FSP feed rate provided an increase in the specific surface area from 217 m2/g at 3 mL/min to 363 m2/g at 7 mL/min. Adopting this knowledge on silica formation under these conditions, the asymmetrical DFSP system was then exploited to regulate the integration of ceria-zirconia with the silica. To restrict the silica from coating the particles during DFSP, the intersection distance along the silica flame was tuned from 18.5 to 28.5 cm, whereas the distance along the ceria-zirconia flame was fixed at 5 cm. It was found that at short intersection distances the ceria-zirconia provided sites for silica nucleation and growth, resulting in high surface-area silica encapsulating the ceria-zirconia. At large intersection distances, encapsulation of the ceria-zirconia by silica was suppressed. An enhanced oxygen storage capacity and basicity along with the small Ni sizes facilitated by the longer intersection distances produced the most selective catalyst for the dry reforming of methane.

Plasma Treating Mixed Metal Oxides to Improve Oxidative Performance via Defect Generation.

The generation of structural defects in metal oxide catalysts offers a potential pathway to improve performance. Herein, we investigated the effect of thermal hydrogenation and low-temperature plasma treatments on mixed SiO2/TiO2 materials. Hydrogenation at 500 °C resulted in the reduction of the material to produce Ti3+ in the bulk TiO2. In contrast, low temperature plasma treatment for 10 or 20 min generated surface Ti3+ species via the removal of oxygen on both the neat and hydrogenated material. Assessing the photocatalytic activity of the materials demonstrated a 40-130% increase in the rate of formic acid oxidation after plasma treatment. A strong relationship between the Ti3+ content and catalyst activity was established, although a change in the Si-Ti interaction after plasma treating of the neat SiO2/TiO2 material was found to limit performance, and suggests that performance is not determined solely by the presence of Ti3+.

Modulating Activity through Defect Engineering of Tin Oxides for Electrochemical CO2 Reduction.

The large-scale application of electrochemical reduction of CO2, as a viable strategy to mitigate the effects of anthropogenic climate change, is hindered by the lack of active and cost-effective electrocatalysts that can be generated in bulk. To this end, SnO2 nanoparticles that are prepared using the industrially adopted flame spray pyrolysis (FSP) technique as active catalysts are reported for the conversion of CO2 to formate (HCOO-), exhibiting a FEHCOO - of 85% with a current density of -23.7 mA cm-2 at an applied potential of -1.1 V versus reversible hydrogen electrode. Through tuning of the flame synthesis conditions, the amount of oxygen hole center (OHC; Sn≡O●) is synthetically manipulated, which plays a vital role in CO2 activation and thereby governing the high activity displayed by the FSP-SnO2 catalysts for formate production. The controlled generation of defects through a simple, scalable fabrication technique presents an ideal approach for rationally designing active CO2 reduction reactions catalysts.