Giant Tunability of the Two-Dimensional Electron Gas at the Interface of γ-Al2O3/SrTiO3.

Two-dimensional electron gases (2DEGs) formed at the interface between two oxide insulators provide a rich platform for the next generation of electronic devices. However, their high carrier density makes it rather challenging to control the interface properties under a low electric field through a dielectric solid insulator, that is, in the configuration of conventional field-effect transistors. To surpass this long-standing limit, we used ionic liquids as the dielectric layer for electrostatic gating of oxide interfaces in an electric double layer transistor (EDLT) configuration. Herein, we reported giant tunability of the physical properties of 2DEGs at the spinel/perovskite interface of γ-Al2O3/SrTiO3 (GAO/STO). By modulating the carrier density thus the band filling with ionic-liquid gating, the system experiences a Lifshitz transition at a critical carrier density of 3.0 × 1013 cm-2, where a remarkably strong enhancement of Rashba spin-orbit interaction and an emergence of Kondo effect at low temperatures are observed. Moreover, as the carrier concentration depletes with decreasing gating voltage, the electron mobility is enhanced by more than 6 times in magnitude, leading to the observation of clear quantum oscillations. The great tunability of GAO/STO interface by EDLT gating not only shows promise for design of oxide devices with on-demand properties but also sheds new light on the electronic structure of 2DEG at the nonisostructural spinel/perovskite interface.

Lignin-Based Polyols with Controlled Microstructure by Cationic Ring Opening Polymerization.

Lignin-based polyols (LBPs) with controlled microstructure were obtained by cationic ring opening polymerization (CROP) of oxiranes in an organosolv lignin (OL) tetrahydrofuran (THF) solution. The control on the microstructure and consequently on the properties of the LBPs such as hydroxyl number, average molecular weight, melting, crystallization and decomposition temperatures, are crucial to determine the performance and application of the derived-products. The influence of key parameters, for example, molar ratio between the oxirane and the hydroxyl groups content in OLO, initial OL concentration in THF, temperature, specific flow rate and oxirane nature has been investigated. LBPs with hydroxyl numbers from 35 to 217 mg KOH/g, apparent average Mw between 5517 and 52,900 g/mol and melting temperatures from -8.4 to 18.4 °C were obtained. The CROP procedure allows obtaining of tailor-made LBPs for specific applications in a very simple way, opening the way to introduce LBPs as a solid alternative to substitute currently used fossil-based polyols.

Efficient bulky phosphines for the selective telomerization of 1,3-butadiene with methanol.

A series of bulky phosphines containing substituted biphenyl, 2-methylnaphthyl, or 2,7-di-tert-butyl-9,9-dimethylxanthene moiety were prepared. They were used in the preparation of new monophosphine-palladium(0)-dvds complexes, which were employed as catalysts for the selective telomerization of 1,3-butadiene with methanol to obtain 1-methoxyocta-2,7-diene (1-MOD), the key intermediate in the Dow 1-octene process. Several ligands showed improved selectivity and yield compared to that of the benchmark ligand PPh(3). Especially 2,7-di-tert-butyl-9,9-dimethylxanthen-4-yl-diphenylphosphine (4, "mono-xantphos") stands out as an excellent ligand in terms of yield, selectivity, and stability.

Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation.

A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 °C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO)2] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.

Elucidating the ionic liquid distribution in monolithic SILP hydroformylation catalysts by magnetic resonance imaging.

Monolithic silicon carbide supported ionic liquid-phase (SILP) Rh-catalysts have very recently been introduced for gas-phase hydroformylation as an important step toward industrial upscaling. This study investigates the monolithic catalyst system in combination with different impregnation procedures with non-invasive magnetic resonance imaging (MRI). The findings were supported by X-ray microtomography (micro-CT) data of the monolithic pore structure and a catalytic performance test of the catalyst system for 1-butene gas-phase hydroformylation. MRI confirmed a homogeneous impregnation of the liquid phase throughout the full cross-section of the cylindrical monoliths. Consistent impregnations from one side to the other of the monoliths were achieved with a stabilizer in the system that helped preventing inhomogeneous rim formation. External influences relevant for industrial application, such as long-term storage and temperature exposure, did not affect the homogeneous liquid-phase distribution of the catalyst. The work elucidates important parameters to improve liquid-phase catalyst impregnation to obtain efficient monolithic catalysts for industrial exploitation in gas-phase hydroformylation as well as other important industrial processes.

Chemoselective hydrogenation of arenes by PVP supported Rh nanoparticles.

Polyvinylpyrrolidone-stabilized Rh nanoparticles (RhNPs/PVP) of ca. 2.2 nm in size were prepared by the hydrogenation of the organometallic complex [Rh(η3-C3H5)3] in the presence of PVP and evaluated as a catalyst in the hydrogenation of a series of arene substrates as well as levulinic acid and methyl levulinate. The catalyst showed excellent activity and selectivity towards aromatic ring hydrogenation compared to other reported transition metal-based catalysts under mild reaction conditions (room temperature and 1 bar H2). Furthermore, it was shown to be a highly promising catalyst for the hydrogenation of levulinic acid and methyl levulinate in water leading to quantitative formation of the fuel additive γ-valerolactone under moderate reaction conditions compared to previously reported catalytic systems.

Silver nanoparticles supported on alumina--a highly efficient and selective nanocatalyst for imine reduction.

Silver nanoparticles supported on alumina were prepared and tested in the catalytic reduction of various imines to primary and secondary amines and were shown to be exceptionally active and chemoselective. Furthermore, the catalytic activity of the prepared nanocatalyst was also tested in the synthesis of secondary amines from primary amines in a tandem reaction protocol (oxidation-imination-reduction) using air and molecular hydrogen as oxidizing and reducing agents, respectively. The reported synthesis is performed under mild reaction conditions, which complies with the demands of modern organic synthesis. Due to the mild reaction conditions and high conversion as well as high selectivity, we consider that the utilization of silver nanoparticles supported on alumina represents an attractive and environmentally friendly alternative to the current synthesis of N-alkyl amines.

Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes.

Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic and aliphatic aldehydes achieving excellent results in terms of both conversion and selectivity.

Carbon-supported palladium and ruthenium nanoparticles: application as catalysts in alcohol oxidation, cross-coupling and hydrogenation reactions.

In the last fifteen-years, the application of metal nanoparticles as catalysts in organic synthesis has received a renewed interest. Therefore, much attention is currently being paid to the synthesis of metal nanoparticles in order to achieve the control of their characteristics in terms of size, shape and surface chemistry. Besides this, the recyclability as well as the recovery from the reaction medium still remain the major drawbacks to widespread the use of nanoparticles in catalysis. To overcome these problems, the immobilization of metal nanoparticles on solid supports appears as a promising alternative. In that context, carbon materials offer several advantages as solid supports such as availability, relatively low cost, high mechanical strength, chemical stability, and a pore structure along with an attractive surface chemistry which allows easy modifications, such as its functionalization, to suit the nanoparticles immobilization needs. Among the transition metals Palladium and Ruthenium are widely employed as efficient catalysts in many reactions. Herein, the most recent advances, from recent papers and patents, in relation to the preparation of carbon-supported Pd or Ru nanoparticles systems as well as their application as catalysts in alcohol oxidation, cross-coupling or hydrogenation reactions, are reviewed.

New alkyl derivatives phosphine sulfonate (P-O) ligands. Catalytic activity in Pd-catalysed Suzuki-Miyaura reactions in water.

Two novel bis(o-methoxyphenyl) phosphinoalkylsulfonate (P-O) ligands have been prepared through a new and sustainable synthetic route; they are air stable as well as water soluble and have been applied in Pd-catalysed Suzuki-Miyaura cross-coupling reactions in neat water in conjunction with microwave heating.

Synthesis and characterization of palladium(II) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation.

The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl)phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2 lambda 4,4 lambda 4-diphosphoniumbicyclo[3.1.1]heptane-bis(PF6) ((o-MeO-PCP)(PF6)2) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl2 and Pd(OAc)2 to give [PdCl2(o-MeO-PCP)](PF6)2 (1a), PdCl2(rac-o-MeO-bdpp) (1b), [Pd(OAc)2(o-MeO-PCP)](PF6)2 (2a) and Pd(OAc)2(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The Pd(II) complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol(-1) with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol(-1) with the diphosphine catalysts.