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.

Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts.

The development of a circular economy is a key target to reduce our dependence on fossil fuels and create more sustainable processes. Concerning hydrogen as an energy vector, the use of liquid organic hydrogen carriers is a promising strategy, but most of them present limitations for hydrogen release, such as harsh reaction conditions, poor recyclability, and low-value byproducts. Herein, we present a novel sustainable methodology to produce value-added silicon precursors and concomitant hydrogen via dehydrogenative coupling by using an air- and water-stable cobalt-based catalyst synthesized from cheap and commercially available starting materials. This methodology is applied to the one-pot synthesis of a wide range of alkoxy-substituted silanes using different hydrosilanes and terminal alkenes as reactants in alcohols as green solvents under mild reaction conditions (room temperature and 0.1 mol % cobalt loading). We also demonstrate that the selectivity toward hydrosilylation/hydroalkoxysilylation can be fully controlled by varying the alcohol/water ratio. This implies the development of a circular approach for hydrosilylation/hydroalkoxysilylation reactions, which is unprecedented in this research field up to date. Kinetic and in situ spectroscopic studies (electron paramagnetic resonance, nuclear magnetic resonance, and electrospray ionization mass spectrometry), together with density functional theory simulations, further provide a detailed mechanistic picture of the dehydrogenative coupling and subsequent hydrosilylation. Finally, we illustrate the application of our catalytic system in the synthesis of an industrially relevant polymer precursor coupled with the production of green hydrogen on demand.

Tailoring the electron density of cobalt oxide clusters to provide highly selective superoxide and peroxide species for aerobic cyclohexane oxidation.

The catalytic aerobic cyclohexane oxidation to cyclohexanol and cyclohexanone (KA oil) is an industrially relevant reaction. This work is focused on the synthesis of tailor-made catalysts based on the well-known Co4O4 core in order to successfully deal with cyclohexane oxidation reaction. The catalytic activity and selectivity of the synthesized catalysts can be correlated with the electronic density of the cluster, modulated by changing the organic ligands. This is not trivial in cyclohexane oxidation. Furthermore, the reaction mechanism is discussed on the basis of kinetics and spin trapping experiments, confirming that the electronic density of the catalyst has a clear influence on the distribution of the reaction products. In addition, in situ Raman spectroscopy was used to characterize the oxygen species formed on the cobalt cluster during the oxidation reaction. Altogether, it can be concluded that the catalyst with the highest oxidation potential promotes the formation of peroxide and superoxide species, which is the best way to oxidize inactivated CH bonds in alkanes. Finally, based on the results of the mechanistic studies, the contribution of these cobalt oxide clusters in each single reaction step of the whole process has been proposed.

Synthesis, Characterization and Antiproliferative Evaluation of Pt(II) and Pd(II) Complexes with a Thiazine-Pyridine Derivative Ligand.

Chemical, pharmacological, and clinical research on anticancer coordination complexes has led to noteworthy anticancer drugs such as cisplatin, carboplatin and oxaliplatin. Although these compounds are effective chemotherapeutic agents in the treatment of different tumors, they are associated with high toxicity and numerous side effects. Several studies have shown that the range of platinum complexes with antitumor activity is not limited to structural analogs of cisplatin. Therefore, the development of convenient anticancer drugs that can be effectively used for the treatment of human tumors has become the main goal of most research groups in this field. In this sense, active platinum complexes without NH groups, transplatinum complexes, multinuclear complexes, cationic complexes, and several classes of palladium(II) complexes have emerged. Herein, the synthesis and characterization of two Pt(II) or Pd(II) complexes with PyTz (2-(2-pyridyl)iminotetrahydro-1,3-thiazine), a thiazine derivative ligand, with the formula [MCl2(PyTz)]·C2H6O (M = Pt(II) or Pd(II)) were reported. The potential anticancer ability of both complexes was evaluated in epithelial cervix carcinoma HeLa, human ovary adenocarcinoma SK-OV-3, human histiocytic lymphoma U-937, and human promyelocytic leukemia HL-60 cell lines. Interestingly, the Pt(II) complex showed great cytotoxic potential against all tumor cell lines tested, whereas the Pd(II) complex displayed slight antitumor actions.

Cobalt Metal-Organic Framework Based on Layered Double Nanosheets for Enhanced Electrocatalytic Water Oxidation in Neutral Media.

A new cobalt metal-organic framework (2D-Co-MOF) based on well-defined layered double cores that are strongly connected by intermolecular bonds has been developed. Its 3D structure is held together by π-π stacking interactions between the labile pyridine ligands of the nanosheets. In aqueous solution, the axial pyridine ligands are exchanged by water molecules, producing a delamination of the material, where the individual double nanosheets preserve their structure. The original 3D layered structure can be restored by a solvothermal process with pyridine, so that the material shows a "memory effect" during the delamination-pillarization process. Electrochemical activation of a 2D-Co-MOF@Nafion-modified graphite electrode in aqueous solution improves the ionic migration and electron transfer across the film and promotes the formation of the electrocatalytically active cobalt species for the oxygen evolution reaction (OER). The so-activated 2D-Co-MOF@Nafion composite exhibits an outstanding electrocatalytic performance for the OER at neutral pH, with a TOF value (0.034 s-1 at an overpotential of 400 mV) and robustness superior to those reported for similar electrocatalysts under similar conditions. The particular topology of the delaminated nanosheets, with quite distant cobalt centers, precludes the direct coupling between the electrocatalytically active centers of the same sheet. On the other hand, the increase in ionic migration across the film during the electrochemical activation stage rules out the intersheet coupling between active cobalt centers, as this scenario would impair electrolyte permeation. Altogether, the most plausible mechanism for the O-O bond formation is the water nucleophilic attack to single Co(IV)-oxo or Co(III)-oxyl centers. Its high electrochemical efficiency suggests that the presence of nitrogen-containing aromatic equatorial ligands facilitates the water nucleophilic attack, as in the case of the highly efficient cobalt porphyrins.

Cobalt Metal-Organic Framework Based on Two Dinuclear Secondary Building Units for Electrocatalytic Oxygen Evolution.

The synthesis of a new microporous metal-organic framework (MOF) based on two secondary building units, with dinuclear cobalt centers, has been developed. The employment of a well-defined cobalt cluster results in an unusual topology of the Co2-MOF, where one of the cobalt centers has three open coordination positions, which has no precedent in MOF materials based on cobalt. Adsorption isotherms have revealed that Co2-MOF is in the range of best CO2 adsorbents among the carbon materials, with very high CO2/CH4 selectivity. On the other hand, dispersion of Co2-MOF in an alcoholic solution of Nafion gives rise to a composite (Co2-MOF@Nafion) with great resistance to hydrolysis in aqueous media and good adherence to graphite electrodes. In fact, it exhibits high electrocatalytic activity and robustness for the oxygen evolution reaction (OER), with a turnover frequency number value superior to those reported for similar electrocatalysts. Overall, this work has provided the basis for the rational design of new cobalt OER catalysts and related materials employing well-defined metal clusters as directing agents of the MOF structure.