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Copper single-site catalysts supported on Zr-based metal-organic frameworks (MOFs) are well-known systems in which the nature of the active sites has been deeply investigated. Conversely, the redox chemistry of the Ce-counterparts is more limited, because of the often-unclear Cu2+/Cu+ and Ce4+/Ce3+ pairs behavior. Herein, we studied a novel Cu2+ single-site catalyst supported on a defective Ce-MOF, Cu/UiO-67(Ce), as a catalyst for the CO oxidation reaction. Based on a combination of in situ DRIFT and operando XAS spectroscopies, we established that Cu+ sites generated during catalysis play a pivotal role. Moreover, the oxygen vacancies associated with Ce3+ sites and presented in the defective Cu/UiO-67(Ce) material are able to activate the O2 molecules, closing the catalytic cycle. The results presented in this work open a new route for the design of active and stable single-site catalysts supported on defective Ce-MOFs.
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Zr-based metal-organic frameworks (MOFs) are excellent heterogeneous porous catalysts due to their thermal stability. Their tunability via node and linker modifications makes them amenable for theoretical studies on catalyst design. However, detailed benchmarks on MOF-based reaction mechanisms combined with kinetics analysis are still scarce. Thus, we here evaluate different computational models and density functional theory (DFT) methods followed by kinetic Monte Carlo studies for a case reaction relevant in biomass upgrading, i.e., the conversion of methyl levulinate to γ-valerolactone catalyzed by UiO-66. We show the impact of cluster versus periodic models, the importance of the DF of choice, and the direct comparison to experimental data via simulated kinetics data. Overall, we found that Perdew-Burke-Ernzerhof (PBE), a widely employed method in plane-wave periodic calculations, greatly overestimates reaction rates, while M06 with cluster models better fits the available experimental data and is recommended whenever possible.
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We print a tunable photopolymer (photopolymer dispersed liquid crystal -PDLC), using the laser-induced direct transfer technique without absorber layer, which was a challenge for this technique given the low absorption and high viscosity of PDLC, and which had not been achieved so far to our knowledge. This makes the LIFT printing process faster and cleaner and achieves a high-quality printed droplet (aspheric profile and low roughness). A femtosecond laser was needed to reach sufficiently peak energies to induce nonlinear absorption and eject the polymer onto a substrate. Only a narrow energy window allows the material to be ejected without spattering.
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We report the first examples of the use of a new class of ligands (NOBINAc) for performing asymmetric C-H activations using palladium catalysts. These ligands combine the axial chirality of binaphthyl scaffolds with the bifunctional and bidentate coordination properties of mono-N-protected amino acids (MPAAs), which are well-known to favor Pd-promoted C-H activations via concerted metalation-deprotonation mechanisms. We demonstrate that our new ligands enable substantially higher enantioselectivities than MPAAs in the assembly of 2-benzazepines through formal (5 + 2) cycloadditions between homobenzyltriflamides or o-methylbenzyltriflamides and allenes.
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Aminas , Paládio , Paládio/química , Estereoisomerismo , Reação de Cicloadição , Ligantes , Catálise , AminoácidosRESUMO
Metal-organic frameworks (MOFs) are gaining importance in the field of biomass conversion and valorization due to their porosity, well-defined active sites, and broad tunability. But for a proper catalyst design, we first need detailed insight of the system at the atomic level. Herein, we present the reaction mechanism of methyl levulinate to γ-valerolactone on Zr-based UiO-66 by means of periodic density functional theory (DFT). We demonstrate the role of Zr-based nodes in the catalytic transfer hydrogenation (CTH) and cyclization steps. From there, we perform a computational screening to reveal key catalyst modifications to improve the process, such as node doping and linker exchange.
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Diffraction gratings are recorded in a holographic photopolymer containing nematic liquid crystal and peppermint oil. The presence of the oil modifies the polymerization and the holographic response. The composite containing oil adulterated with triethyl citrate obtains a diffraction efficiency related to the oil's purity. The results obtained suggest the possibility of developing a holographic chemical analysis method for quality control of raw materials.
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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.
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Photopolymers have become an important recording material for many applications, mainly related to holography. Their flexibility to change the chemical composition together with the optical properties made them a versatile holographic recording material. The introduction of liquid crystal molecules in a photopolymer based on multifunctional monomer provides us the possibility to generate tunable holograms. The switchable holographic elements are a key point for see-through applications. In this work, we optimize the holographic polymer-dispersed liquid crystals composition to improve the performance of tunable waveguide couplers based on transmission gratings and specifically their response under an applied electric field. A variation around 60% in the transmission efficiency was achieved.
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Dianionic hyponitrite (N2 O22- ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases. In this work, we examine the gas-solid reaction of nitric oxide with the metal-organic framework CuI -ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N2 O2.- intermediate. These results highlight the advantage provided by site-isolation in metal-organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one-electron couple in these enzymes.
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A combined computational and experimental approach demonstrates the accelerating role of deaggregation agents, especially HMPA, in the Li-catalysed hydrosilylation of acetophenone in THF solution under very mild conditions.
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Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal-organic framework (MOF) via cation exchange and subsequent oxidation at 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol at 150-200 °C. At 150 °C and 1 bar methane, approximately a third of the copper centers are involved in converting methane to methanol. Methanol productivity increased by 3-4-fold and selectivity increased from 70% to 90% by increasing the methane pressure from 1 to 40 bar. Density functional theory showed that reaction pathways on various copper sites are able to convert methane to methanol, the copper oxyl sites with much lower free energies of activation. Combining studies of the stoichiometric activity with characterization by in situ X-ray absorption spectroscopy and density functional theory, we conclude that dehydrated dinuclear copper oxyl sites formed after activation at 200 °C are responsible for the activity.
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Production of 1-butene, a major monomer in polymer industry, is dominated by homogeneous protocols via ethylene dimerization. Homogeneous catalysts can achieve high selectivity but require large amounts of activators and solvents, and exhibit poor recyclability; in turn, heterogeneous systems are robust but lack selectivity. Here we show how the precise engineering of metal-organic frameworks (MOFs) holds promise for a sustainable process. The key to the (Ru)HKUST-1 MOF activity is the intrapore reactant condensation that enhances ethylene dimerization with high selectivity (> 99% 1-butene) and high stability (> 120 h) in the absence of activators and solvents. According to spectroscopy, kinetics, and modeling, the engineering of defective nodes via controlled thermal approaches rules the activity, while intrapore ethylene condensation accounts for selectivity and stability. The combination of well-defined actives sites with the concentration effect arising from condensation regimes paves the way toward the development of robust MOF catalysts for diverse gas-phase reactions.
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The storage of volume holographic reflection gratings in low-toxicity photopolymers represents a challenge at present since they can be used in many important applications such as biosensors and holographic optical elements. In this context, an acrylate-based photopolymer developed in our research group was employed to study the recording of unslanted holographic reflection gratings at high spatial frequencies. The optimal preparation conditions of the photopolymer layers were determinated. The diffraction efficiencies are measured in both recording and curing stage and a comparative study of these values was realized. In addition, a theoretical study using Kogelnik's coupled wave theory was carried out with the aim of understanding the diffraction efficiency behaviour of both processes. In this work, a maximum diffraction efficiency of 14.1% was reached after a curing process in 150 µm layers at a recording wavelength of 488 nm. This value represents a good result compared to that reported in the literature and opens the way to reflection mode holography research using low-toxicity material.
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Tert-Butylthiol (TBT) and tetrahydrothiophene (THT) are odorant substances added to natural gas and liquefied petroleum gas to help their detection by the human smell. In this research, TBT and THT are incorporated into a holographic polymer-dispersed liquid crystal and their influence in the main holographic characteristics of the photopolymer are studied in order to open the way towards the design of a holographic sensor to detect natural gas and liquefied petroleum gas.
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A holographic polymer dispersed liquid crystal (HPDLC) is used to record holographic diffraction gratings. Several mixtures of nematic liquid crystals (LC) are used as components of the HPDLC to evaluate their influence in static and dynamic basic properties. The diffraction efficiency obtained in the reconstruction of the holograms is evaluated to compare the influence of the different LC. Additionally, the samples are exposed to a variable electric field and the diffracted light intensity as a function of the applied voltage is measured to evaluate the influence of the LC. The results obtained show significant differences depending on the LC incorporated to the photopolymer.
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Truxene derivatives, due to their molecular structure and properties, are good candidates for the passivation of defects when deposited onto hybrid lead halide perovskite thin films. Moreover, their semiconductor characteristics can be tailored through the modification of their chemical structure, which allows-upon light irradiation- the interfacial charge transfer between the perovskite film and the truxene molecules. In this work, we analysed the use of the molecules as surface passivation agents and their use in complete functional solar cells. We observed that these molecules reduce the non-radiative carrier recombination dynamics in the perovskite thin film through the supramolecular complex formation between the Truxene molecule and the Pb2+ defects at the perovskite surface. Interestingly, this supramolecular complexation neither affect the carrier recombination kinetics nor the carriers collection but induced noticeable hysteresis on the photocurrent vs voltage curves of the solar cells under 1 sun illumination.
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Increasing the activity of the nitrogen reduction reaction while slowing the detrimental hydrogen evolution reaction is a key challenge in current electrocatalysis to provide a sustainable route to ammonia. Recently, nanoparticles in ionic liquid (IL) environments have been found to boost the selectivity of electrochemical synthesis of ammonia from dinitrogen at room temperature. Here, we use for the first time a fully atomistic representation of metal-IL interfaces at the density functional theory level to understand experimental evidence, with particular focus on the rate and selectivity determining formation of N2H intermediates compared to hydrogen evolution. We find that decorating the metal surface with fluorinated ILs creates specific H-bond interactions between Ru-N2H and IL anions, stabilizing this intermediate and thus driving the selectivity of the electrochemical process.
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Palladium-catalysed cross-coupling reactions, central tools in fine-chemical synthesis, predominantly employ soluble metal complexes despite recognized challenges with product purification and catalyst reusability1-3. Attempts to tether these homogeneous catalysts on insoluble carriers have been thwarted by suboptimal stability, which leads to a progressively worsening performance due to metal leaching or clustering4. The alternative application of supported Pd nanoparticles has faced limitations because of insufficient activity under the mild conditions required to avoid thermal degradation of the substrates or products. Single-atom heterogeneous catalysts lie at the frontier5-18. Here, we show that the Pd atoms anchored on exfoliated graphitic carbon nitride (Pd-ECN) capture the advantages of both worlds, as they comprise a solid catalyst that matches the high chemoselectivity and broad functional group tolerance of state-of-the-art homogeneous catalysts for Suzuki couplings, and also demonstrate a robust stability in flow. The adaptive coordination environment within the macroheterocycles of ECN facilitates each catalytic step. The findings illustrate the exciting opportunities presented by nanostructuring single atoms in solid hosts for catalytic processes that remain difficult to heterogenize.
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The spontaneous rearrangement of allylic azides is thought to be a sigmatropic reaction. Presented herein is a detailed investigation into the rearrangement of several allylic azides. A combination of experiments including equilibrium studies, kinetic analysis, density functional theory calculations, and selective 15N-isotopic labeling are included. We conclude that the Winstein rearrangement occurs by the assumed sigmatropic pathway under most conditions. However, racemization was observed for some cyclic allylic azides. A kinetic analysis of this process is provided, which supports a previously undescribed ionic pathway.
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Compostos Alílicos/química , Azidas/química , Catálise , EstereoisomerismoRESUMO
Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr6O8. Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr6O8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an SN2 mechanism.