Ultralow-Loading and High-Performing Ionic Liquid-Immobilizing Rhodium Single-Atom Catalysts for Hydroformylation.

We have developed a Keggin polyoxometalate (POM)-based ionic-liquid (IL)-immobilizing rhodium single-atom Rh catalyst (MTOA)5 [SiW11 O39 Rh] (MOTA=methyltrioctylammonium cation) that can afford exceptionally high catalytic activity for the hydroformylation of alkenes to produce aldehydes at an ultralow loading of Rh (ca. 3 ppm). For styrene hydroformylation, both the conversion and the yield of the aldehyde can reach almost 99 %, and a TOF as high as 9000 h-1 was obtained without using any phosphine ligand in the reaction process. Further characterization by FTIR, ICP and ESI-MS analysis revealed that the single Rh atom was incorporated in the lacunary POM anions. In particular, the bulky IL cation can play an additional role in stabilizing Rh species and thus prevent aggregation and leaching of Rh species. The IL catalyst was miscible with n-hexane at temperatures; this contributed to exceptionally high activity for hydroformylation even at ultra-low loading of IL catalyst.

High Proton-Conductivity in Covalently Linked Polyoxometalate-Organoboronic Acid-Polymers.

The controlled bottom-up design of polymers with metal oxide backbones is a grand challenge in materials design, as it could give unique control over the resulting chemical properties. Herein, we report a 1D-organo-functionalized polyoxometalate polymer featuring a purely inorganic backbone. The polymer is self-assembled from two types of monomers, inorganic Wells-Dawson-type polyoxometalates, and aromatic organo-boronates. Their covalent linkage results in 1D polymer strands, which combine an inorganic oxide backbone (based on B-O and Nb-O linkages) with functional organic side-chains. The polymer shows high bulk proton conductivity of up to 1.59×10-1  S cm-1 at 90 °C and 98 % relative humidity. This synthetic approach could lead to a new class of organic-inorganic polymers where function can be designed by controlled tuning of the monomer units.

Thermoregulated Ionic Liquid-Stabilizing Ru/CoO Nanocomposites for Catalytic Hydrogenation.

Catalytic hydrogenations represent fundamental processes and allow for atom-efficient and clean functional group transformations for the production of chemical intermediates and fine chemicals in chemical industry. Herein, the Ru/CoO nanocomposites have been constructed and applied as nanocatalysts for the hydrogenation of phenols and furfurals into the corresponding cyclohexanols and tetrahydrofurfuryl alcohols, respectively. The functionalized ionic liquid acted not only as a ligand for stabilizing the Ru/CoO nanocatalyst but also as a thermoregulated agent. The as-obtained nanocatalyst showed superior activity, and it could be conveniently recovered via the thermoregulating phase separation. In six recycle experiments, the catalysts maintained excellent performance. It was observed that the catalytic performance highly hinged on the molar ratio of Ru to Co in the nanocatalyst. The catalyst characterization was carried out by high-resolution transmission electron microscopy (HRTEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy, X-ray diffraction, high-resolution mass spectrometry, Fourier transform infrared, nuclear magnetic resonance, and UV-vis. Especially, the characterization by HRTEM and HAADF-STEM images of the nanocatalyst demonstrated that Ru(0) and Co(II) species were distributed uniformly and the Ru and Co(II) species were close to each other. However, Co(0) was generated and an electronic transfer from Co to Ru species could occur under the hydrogenation conditions. The 13C NMR characterization indicated further that Co(II) sites were mainly responsible for phenol adsorption. Meanwhile, the adjacent electron-rich Ru(0) sites can promote H2 dissociation and favor for the sequential hydrogenation.

Controllable Synthesis and Catalytic Performance of Nanocrystals of Rare-Earth-Polyoxometalates.

Large-scale isolation of nanocrystals of rare-earth-polyoxometalates (RE-POMs) catalysts is important in fundamental research and applications. Here, we synthesized a family of monomeric RE-POMs by the self-assembly of Ta/W mixed-addendum POM {P2W15Ta3O62} and rare-earth (RE) ions. These RE-POMs with molecular formulas of [RE(H2O)7]3P2W15Ta3O62· nH2O (RE = Y, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) are all electroneutral molecular clusters, insoluble in water and common organic solvents. The electronic structures, electrochemical properties, and catalytic activities of them have been investigated by experimental and computational methods. In particular, based on a mild and controllable synthetic process, a convenient and controllable approach to prepare nanocrystals and self-organized aggregates of these monomers has been developed. They exhibit remarkable heterogeneous catalytic activity for cyanosilylation. Both the increased Lewis acid strength of RE in the title compounds, as indicated by theoretical calculations, and the decreased particle size contribute to their high catalytic performances.

Lanthanide derivatives of Ta/W mixed-addendum POMs as proton-conducting materials.

Four lanthanide derivatives of Ta-containing POMs [Ln3(H2O)22][P2W15Ta3O62]·nH2O (Ln = La, 1; Ce, 2; Pr, 3; and Nd, 4) were isolated by the self-assembly of Wells-Dawson type Ta/W mixed-addendum POM and lanthanide ions. Compound 1 showed excellent proton conduction performance at high relative humidities (RHs), with conductivity reaching 1.26 × 10-2 S cm-1 at 95 °C under 98% RH.