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The growing demand for new energy sources governs the intensive research into CO2 hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during the reaction and low selectivity. Here, we report a new strategy of controlling the selectivity and stability of bimetallic magnetically recoverable indium-based catalysts deposited onto a solid support. This was accomplished by the introduction of a structural promoter: a branched pyridylphenylene polymer (PPP). The selectivity of methanol formation for this catalyst reached 98.5%, while in the absence of PPP, the catalysts produced a large amount of methane, and the selectivity was about 70.2%. The methanol production rate was higher by a factor of twelve compared to that of a commercial Cu-based catalyst. Along with tuning selectivity, PPP allowed the catalyst to maintain a high stability, enhancing the CO2 sorption capacity and the protection of In against sintering and over-reduction. A careful evaluation of the structure–activity relationships allowed us to balance the catalyst composition with a high level of structural control, providing synergy between the support, magnetic constituent, catalytic species, and the stabilizing polymer layer. We also uncovered the role of each component in the ultimate methanol activity and selectivity. [ABSTRACT FROM AUTHOR]

Development of new microporous organic polymers attracts significant attention due to a wide scope of promising applications. In addition, the synthesis of soluble, non-crosslinking polymers of high surface area and uniform microporosity is very challenging, and the methods for soluble microporous polymers formation are rather limited. In this work, we report a new approach to construct porous polyphenylenes which employs the Diels–Alder polycondensation of multifunctional ethynyl-containing monomers of different spatial architecture with bis(cyclopentadienone)s. The resulting polymers were soluble in common organic solvents, and their structure and properties were assessed by NMR, TGA, DSC, and SEC studies. The polymers demonstrated a specific surface area up to 751 m2·g−1 and ultramicroporous (pore size ≤ 0.6 nm) structure. N2 and CO2 adsorption–desorption data revealed that porosity parameters, e.g., specific surface area and pore sizes, can be tuned selectively by varying the type of monomers and reaction conditions. [ABSTRACT FROM AUTHOR]

CO2 hydrogenation to methanol is an important process that could solve the problem of emitted CO2 that contributes to environmental concern. Here we developed Cr-, Cr-Zn-, and Cr-Ni-containing nanocomposites based on a solid support (SiO2 or Al2O3) with embedded magnetic nanoparticles (NPs) and covered by a cross-linked pyridylphenylene polymer layer. The decomposition of Cr, Zn, and Ni precursors in the presence of supports containing magnetic oxide led to formation of amorphous metal oxides evenly distributed over the support-polymer space, together with the partial diffusion of metal species into magnetic NPs. We demonstrated the catalytic activity of Cr2O3 in the hydrogenation reaction of CO2 to methanol, which was further increased by 50% and 204% by incorporation of Ni and Zn species, respectively. The fine intermixing of metal species ensures an enhanced methanol productivity. Careful adjustment of constituent elements, e.g., catalytic metal, type of support, presence of magnetic NPs, and deposition of hydrophobic polymer layer contributes to the synergetic promotional effect required for activation of CO2 molecules as well. The results of catalytic recycle experiments revealed excellent stability of the catalysts due to protective role of hydrophobic polymer. [ABSTRACT FROM AUTHOR]

Heat-up and hot-injection methods were employed to synthesize Ni nanoparticles (NPs) with narrow size distribution in the presence of hyperbranched pyridylphenylene polymer (PPP) as a stabilizing agent. It was shown that depending on the synthetic method, Ni NPs were formed either in a cross-linked polymer network or stabilized by a soluble hyperbranched polymer. Ni NPs were characterized by a combination of transmission electron microscopy (TEM), scanning TEM, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, and magnetic measurements. The architecture of polymer support was found to significantly effect Ni NPs characteristics and behavior. The Ni NPs demonstrated a high catalytic activity in a model Suzuki–Miyaura cross-coupling reaction. No significant drop in activity was observed upon repeated use after magnetic separation in five consecutive catalytic cycles. We believe that hyperbranched PPP can serve as universal platform for the controllable synthesis of Ni NPs, acting as highly active and stable catalysts. [ABSTRACT FROM AUTHOR]

Hydrodynamic and optical methods were applied to study conformational and physical properties of hyperbranched pyridylphenylene polymers in dilute solutions. The samples were synthesized using Diels-Alder polycyclocondensation. It was demonstrated that hydrodynamic properties of the studied macromolecules were typical for compact non-percolated spheres. Optical and electro-optical methods revealed information regarding the shape and asymmetry of the macromolecules ( p ≈ 1.4). The contributions of optical shape effect to the observed flow birefringence of polypyridylphenylene solutions and intrinsic anisotropy of polarizability were evaluated and analysed. It was shown that varying the polymer composition (i.e. the degree of branching) caused considerable changes in the anisotropy of optical polarizability of the polymers. Dramatic difference of the electro-optical properties in non-polar (toluene) and polar (tetrachloroethane) solvents was found; this difference was related to the orientational correlation of polar solvent molecules with respect to the macromolecules. Dynamic properties were studied by non-equilibrium electric birefringence which had a reasonable agreement with the dimensions estimated from hydrodynamic data. © 2016 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Hydrogenation of levulinic acid (LA) obtained from cellulose biomass is a promising path for production of γ-valerolactone (GVL)—a component of biofuel. In this work, we developed Ru nanoparticle containing nanocomposites based on hyperbranched pyridylphenylene polymer, serving as multiligand and stabilizing matrix. The functionalization of the nanocomposite with sulfuric acid significantly enhances the activity of the catalyst in the selective hydrogenation of LA to GVL and allows the reaction to proceed under mild reaction conditions (100 °C, 2 MPa of H2) in water and low catalyst loading (0.016 mol.%) with a quantitative yield of GVL and selectivity up to 100%. The catalysts were successfully reused four times without a significant loss of activity. A comprehensive physicochemical characterization of the catalysts allowed us to assess structure-property relationships and to uncover an important role of the polymeric support in the efficient GVL synthesis. [ABSTRACT FROM AUTHOR]

Carbon-carbon cross-coupling reactions are among the most important synthetic tools for the preparation of pharmaceuticals and bioactive compounds. However, these reactions are normally carried out using copper, phosphines, and/or amines, which are poisonous for pharmaceuticals. The use of nanocomposite catalysts holds promise for facilitating these reactions and making them more environmentally friendly. In the present work, the PEGylated (PEG stands for poly(ethylene glycol) pyridylphenylene dendrons immobilized on silica loaded with magnetic nanoparticles have been successfully employed for the stabilization of Pd2+ complexes and Pd nanoparticles. The catalyst developed showed excellent catalytic activity in copper-free Sonogashira and Heck cross-coupling reactions. The reactions proceeded smoothly in green solvents at low palladium loading, resulting in high yields of cross-coupling products (from 80% to 97%) within short reaction times. The presence of magnetic nanoparticles allows easy magnetic separation for repeated use without a noticeable decrease of catalytic activity due to the strong stabilization of Pd species by rigid and bulky dendritic ligands. The PEG dendron periphery makes the catalyst hydrophilic and better suited for green solvents. The minor drop in activity upon the catalyst reuse is explained by the formation of Pd nanoparticles from the Pd2+ species during the catalytic reaction. The magnetic separation and reuse of the nanocomposite catalyst reduces the cost of target products as well as energy and material consumption and diminishes residual contamination by the catalyst. These factors as well as the absence of copper in the catalyst makeup pave the way for future applications of such catalysts in cross-coupling reactions. [ABSTRACT FROM AUTHOR]