Synthesis and Characterization of NiMo Catalysts Supported on Fine Carbon Particles for Hydrotreating: Effects of Metal Loadings in Catalyst Formulation

The by-products collected during the synthesis of carbon nanohorns via the arc discharge synthesis method is comprised of other carbon particles (OCP). At a hydrotreating operating temperature of 370°C, preliminary investigations using a bimetallic catalyst with support originating from the fine fractions of other carbon particles (OCPf) and containing 13 wt% Mo and 2.5 wt% Ni resulted in an HDS and HDN conversion of 78 and 25%, respectively. Variation of metal compositions in catalyst formulation and its impact on hydrotreating activity was therefore considered in this study to enhance the hydrotreating activity of OCPf–supported catalyst, and to determine if the best NiMo/OCPf catalyst achieved from this study could be a viable catalyst for hydrotreating applications. The co-incipient wetness impregnation was used in preparing series of hydrotreating catalysts with Ni and Mo loadings within the range of (2.5–5.0 wt%) and (13–26 wt%) respectively. Overall, the catalyst samples with maximum Ni loading of 5.0 wt% and Mo loadings of either 13 or 19 wt% showed higher dispersion and the ability to form a Type II Ni-Mo-S phase with enhanced activity. The effects of metal compositions on both HDS and HDN activities were correlated with their physicochemical properties.

Remarkable Enhancement of Catalytic Activity of Cu-Complexes in the Electrochemical Hydrogen Evolution Reaction (HER) by Using Triply-Fused Porphyrin

Developing efficient molecular catalysts for the electrocatalytic hydrogen evolution reaction (HER) is a highly important goal in contemporary science. We report here on a bimetallic triply fused copper porphyrin complex (1) comprising two monomeric porphyrin units linked through β–β, meso–meso, β′–β′ triple covalent linkages, that exhibits remarkable enhancement of catalytic activity for the electrochemical HER in comparison to the analogous monomeric copper porphyrin complex (2). Spectroscopic characterization, in association with magnetic measurements, clearly establish the ground state structures of both the bimetallic and monometallic complexes as containing two and one copper (II) centers, respectively. The fused metalloporphyrin complex is found to undergo electrochemical reduction at a lower negative applied potential compared to the metalloporphyrin monomer, as evident from the significant anodic shift (~800mV) in the potential of the first reduction process. Electrochemical investigations in the presence of a proton source (trifluoroacetic acid) confirm that the catalytic activity of the fused metalloporphyrin occurs at a significantly lower onset potential, (overpotential decreased by ~320 mV), compared to the non-fused monomer. Controlled potential electrolysis combined with the kinetic analysis of catalysts 1 and 2 confirm the production of hydrogen, with 96% and 71% faradaic efficiencies and turnover numbers of 102 and 18, respectively. Kinetic investigations further reveal an observed rate constant of around 107 (s-1), implying high efficiency of the bimetallic catalyst towards hydrogen evolution reaction. Mechanistic insights are presented by using a combination of UV-vis-NIR and EPR spectroscopy and electrochemistry. Our results thus firmly establish the triply fused porphyrin ligands as candidates for generating highly efficient molecular electrocatalysts in combination with transition metal centers.

Porous Organic Polymer Supported Pd/Cu Bimetallic Catalyst for Heterogeneous Oxidation of Alkynes to 1,2-Diketones

A porous organic polymer (POP-POPh3) was readily prepared by oxidation of POP-PPh3 with H2O2. After coordination with PdCl2 and co-catalyst of CuBr2 precursor, a Pd/Cu bimetals-loaded porous organic polymer (Pd/Cu@POP-POPh3)...

Highly efficient selective hydrogenation of levulinic acid to γ-valerolactone over Cu–Re/TiO2 bimetallic catalysts

Herein, we report a highly efficient and recyclable Cu–Re(1 : 1)/TiO2 bimetallic catalyst for liquid phase hydrogenation of levulinic acid to γ-valerolactone.

Bimetallic PdCo Nanoparticles Loaded in Amine Modified Polyacrylonitrile Hollow Spheres as Efficient Catalysts for Formic Acid Dehydrogenation

Polyacrylonitrile hollow nanospheres (HPAN), derived from the polymerization of acrylonitrile in the presence of polystyrene emulsion (as template), were modified by surface amination with ethylenediamine (EDA), and then used as support for loading Pd or PdCo nanoparticles (NPs). The resultant bimetallic catalyst (named PdCo0.2/EDA-HPAN) can efficiently catalyze the additive-free dehydrogenation of formic acid with very high activity, selectivity and recyclability, showing turnover frequencies (TOF) of 4990 h−1 at 333 K and 915 h−1 at 303 K, respectively. The abundant surface amino groups and cyano group as well as the hollow structure of the support offer a suitable environment for achieving high dispersion of the Pd-based NPs on the surface of EDA-HPAN, thus generating ultra-small bimetallic NPs (bellow 1.0 nm) with high stability. The addition of a small portion of Co may adjust the electronic state of Pd species to a certain extent, which can further improve their capability for the dehydrogenation of formic acid. In addition, the surface amino groups may also play an important role in synergistically activating formic acid to generate formate, thus leading to efficient conversion of formic acid to hydrogen at mild conditions.

Oxidation of Monoethylene Glycol to Glycolic Acid with Gold-Based Catalyst and Glycolic Acid Isolation by Electrodialysis

In this work, a highly selective and active gold-based catalyst for the oxidation of high concentrated monoethylene glycol (MEG) in aqueous solution (3 M, 20 wt%) is described. High glycolic acid (GA) selectivity was achieved under mild reaction conditions. The optimization of the catalyst composition and of the reaction conditions for the oxidation of MEG in semi-batch mode under alkaline conditions led to a GA yield of >80% with a GA selectivity of about 90% in short reaction time. The bimetallic catalyst 0.1 wt% AuPt (9:1)/CeO2 showed very high activity (>2000 mmolMEG/gmetalmin) in the oxidation of MEG and, contrary to other studies, an extremely high educt to metal mole ratio of >25,000 was used. Additionally, the gold–platinum catalyst showed a high GA selectivity over more than 10 runs. A very efficient and highly selective process for the GA production from MEG under industrial relevant reaction conditions was established. In order to obtain a GA solution with high purity for the subsequent polymerization, the received reaction solution containing sodium glycolate, unreacted MEG and sodium oxalate is purified by a novel down-stream process via electrodialysis. The overall GA yield of the process exceeds 90% as unreacted MEG can be recycled.

Leveraging the interplay between homogeneous and heterogeneous catalytic mechanisms: copper-iron nanoparticles working under chemically relevant tumor conditions

The present work sheds light on a generally overlooked issue in the emerging field of bio-orthogonal catalysis within tumor microenvironments (TMEs): the interplay between homogeneous and heterogeneous catalytic processes. In most cases, previous works dealing with nanoparticle-based catalysis in the TME, focus on the effects obtained (e.g. tumor cell death) and attribute the results to heterogeneous processes alone. The specific mechanisms are rarely substantiated and, furthermore, the possibility of a significant contribution of homogeneous processes by leached species –and the complexes that they may form with biomolecules- is neither contemplated nor pursued. Herein, we have designed a bimetallic catalyst nanoparticle containing Cu and Fe species and we have been able to describe the whole picture in a more complex scenario where both homogeneous and heterogeneous processes are coupled and fostered under TME relevant chemical conditions. We investigate the preferential leaching of Cu ions in the presence of a TME overexpressed biomolecule such as glutathione (GSH). We demonstrate that these homogeneous processes initiated by the released by Cu-GSH interactions are in fact responsible for the greater part of the cell death effects found (GSH, a scavenger of reactive oxygen species is depleted and highly active superoxide anions are generated in the same catalytic cycle). The remaining solid CuFe nanoparticle becomes an active catalase-mimicking surrogate able to supply oxygen from oxygen reduced species, such as superoxide anions (by-product from GSH oxidation) and hydrogen peroxide, another species that is enriched in the TME. This enzyme-like activity is essential to sustain the homogeneous catalytic cycle in the oxygen-deprived tumor microenvironment. The combined heterogeneous-homogeneous mechanisms revealed themselves as highly efficient in selectively killing cancer cells, due to their higher GSH levels compared to healthy cell lines.