A tandem process for in situ H2O2 formation coupled with benzyl alcohol oxidation using Pd-Au bimetallic catalysts.

Alcohol oxidation is one of the most important industrial organic reactions. Traditionally, the best-suited catalysts are Pd, Pt and Au supported nanoparticles. The research community has recently started developing strategies for synthesizing carbon-supported Pd/Au bimetallic nanoparticles (NPs), leading to higher activities and selectivities. However, the metallic active species in these catalysts are usually generated using sodium borohydride (NaBH4), which is not synthetically easy to reproduce. In fact, minor modifications in pH, concentration and/or other parameters have a prominent effect on the nature of the promoted material. In this work, a robust process involving dihydrogen flow (H2) at 200 °C as a reducing agent for synthesizing Pd/Au supported bimetallic materials was considered an alternative to the common pathway. The physicochemical properties of the materials derived from different reducing reagents and of varying composition ranges were studied using HR-TEM, XRD, CO chemisorption, and XPS. Their stability and activity were also tested for benzyl alcohol oxidation to benzaldehyde under mild reaction conditions (60 °C, water as the solvent, and PO2 = 1.5 bar). Notably, a catalyst from the hydrogen reduction process with a metal composition of 0.8%Pd-0.2%Au/C consisting of bimetallic clusters (≈1.5 nm) proved to be the best material (C = 94%, S = 99%). Catalytic performances were strongly correlated with structural properties, such as nanoparticle size and distribution, which, in turn, were affected by the reduction step and the metal composition range. Finally, the influence of oxidants on benzyl alcohol oxidation has also been studied, along with the first approach for the tandem in situ formation of H2O2 coupled with alcohol oxidation.

TiO2-Supported Pd as an Efficient and Stable Catalyst for the Mild Hydrotreatment of Tar-Type Compounds.

The mild hydrotreatment of a model mixture of tar-type compounds (i.e., naphthalene, 1-methylnaphthalene, acenaphthylene, and phenanthrene) to produce partially hydrogenated products in the range of C9-C15 was studied over Pd supported on TiO2 possessing different crystalline phases. Pd-based catalysts were prepared and characterized by ICP analysis, XRD, N2 adsorption isotherms, HR-TEM, and NH3-TPD, among others. The hydrotreatment activity and selectivity towards the desired hydrogenated products (i.e., tetralin and others) increased with both the acidity and surface area of the catalyst, along with the presence of small and well distributed Pd nanoparticles. For the selected 1.3 wt% Pd/TiO2 nano catalyst, the operational conditions for maximizing tar conversion were found to be 275 °C, 30 bar of H2, and 0.2 g of catalyst for 7 h. The catalyst revealed remarkable hydrotreatment activity and stability after several reuses with practically no changes in TiO2 structure, quite low carbon deposition, and any Pd leaching detected, thus maintaining both a small Pd particle size and adequate distribution, even after regeneration of the catalyst. Additionally, the Pd/TiO2 nano catalyst was demonstrated to be more active than other commonly used metal/alumina and more selective than metal/USY zeolites in the mild hydrotreatment of tar-type compounds, thus providing an efficient catalytic route for obtaining partially hydrogenated C9-C15 hydrocarbons useful as jet-fuel components or additives (improvers), as well as chemicals and solvents for industrial applications.

Conversion of Glycerol to Value Added Products in a Semi-Continuous Batch Reactor Using Noble Metals Supported on ZSM-11 Zeolite.

Au, Pt, and Pd supported on ZSM-11 microporous zeolite were investigated as catalysts for glycerol (GLY) oxidation towards higher value added products. ZSM-11 was synthesized by hydrothermal treatment. Subsequently, ion exchange with NH4Cl was performed to recover acidic sites and then, Au, Pt, and Pd were incorporated onto this material by wet impregnation procedure. After thermal treatment of desorption and calcination, the corresponding Au, Pt, and Pd-ZSM-11 catalysts were obtained. These materials were characterized by different techniques, such as XRD, ICP, TEM- XEDS, and XPS, and were evaluated in the glycerol oxidation reaction by using alkaline medium and molecular oxygen as oxidizing agent. The higher conversion of GLY (66.5 mol.%) was reached for the Pt-ZSM-11 catalyst with moderate selectivity towards lactic acid (LA), while the bimetallic Au-Pt-ZSM-11 catalyst offered high selectivity to LA at moderate GLY conversion. Optimization of the main reaction parameters (i.e., temperature, reaction time and NaOH/GLY ratio) was carried out to maximize the selectivity towards the LA desired product. Thus, LA selectivity values close to 55% at GLY conversion >65% can be reached by using Pt-ZSM-11 as a catalyst under mild reaction conditions.

MOF-Mediated Synthesis of Supported Fe-Doped Pd Nanoparticles under Mild Conditions for Magnetically Recoverable Catalysis*.

Metal-organic framework (MOF)-driven synthesis is considered as a promising alternative for the development of new catalytic materials with well-designed active sites. This synthetic approach is used here to gradually transform a new bimetallic MOF, with Pd and Fe as the metal components, by the in situ generation of aniline under mild conditions. This methodology results in a compositionally homogeneous nanocomposite formed by Fe-doped Pd nanoparticles that, in turn, are supported on iron oxide-doped carbon. The nanocomposite has been fully characterized by several techniques such as IR and Raman spectroscopy, TEM, XPS, and XAS. The performance of this nanocomposite as an heterogeneous catalyst for hydrogenation of nitroarenes and nitrobenzene coupling with benzaldehyde has been evaluated, proving it to be an efficient and reusable catalyst.

Redox tuning and species distribution in Maya Blue-type materials: a reassessment.

Maya Blue-type specimens prepared from indigo (1 wt %) plus kaolinite, montmorillonite, palygorskite, sepiolite, and silicalite are studied. Liquid chromatography with diode array detection, ultra-performance liquid chromatography coupled with mass spectrometry, and pyrolysis-silylation gas chromatography-mass spectrometry analyses of the extracts from these specimens combined with spectral and solid-state voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy techniques provide evidence for the presence of a significant amount of dehydroindigo and isatin accompanying indigo and other minority organic compounds in all samples. Solid-state electrochemistry data permits the estimatation of indigo loading in archeological Maya Blue, which is in the range of 0.2 to 1.5 wt %. These results support a view of 'genuine' Maya Blue-type materials as complex polyfunctional organic-inorganic hybrids.

Gold supported on a mesoporous CeO2 matrix as an efficient catalyst in the selective aerobic oxidation of aldehydes in the liquid phase.

Gold supported on CeO2 catalyses the selective aerobic oxidation of aliphatic and aromatic aldehydes better than other reported catalysts such as Pt/C/Bi materials; the activity is due to the nanometric particle size of Au and CeO2.

Al-free Sn-Beta zeolite as a catalyst for the selective reduction of carbonyl compounds (Meerwein-Ponndorf-Verley reaction).

The catalytic activity of Sn-Beta zeolite in the Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl compounds with secondary alcohols was performed with quantitative yields to the corresponding alcohol. This heterogeneous catalyst exhibits activities and selectivities not observed before with other Me-zeolites.