Unlocking the Potential of MXene in Catalysis: Decorated Mo2CTx Catalyst for Ammonia Synthesis under Mild Conditions.

Ammonia, which is one of the most important chemicals for the synthesis of dyes, pharmaceuticals, and fertilizers, is produced by the reaction of molecular hydrogen with nitrogen, over an iron-based catalyst at 400-500 °C under pressure of over 100 bar. Decreasing the operating temperature and pressure of this highly energy-intensive process, developed by Haber and Bosch over 100 years ago, would decrease energy consumption in the world. In this work, we used two-dimensional Mo2CTx MXene as a support for a cobalt-based catalyst. The MXene functionalized by Co showed catalytic activity for ammonia synthesis from H2 and N2 at temperatures as low as 250 °C, without any pretreatment. The developed catalyst was highly active for ammonia synthesis, demonstrating a high rate of up to 9500 µmol g-1active phase h-1 at 400 °C under ambient pressure in steady-state conditions, and did not suffer from any deactivation after 15 days of reaction. The apparent activation energy (Ea) was found to be in the range of 68-74 kJ mol-1, which is in line with values reported for highly active catalysts. This improved catalyst may decrease the energy consumption in the synthesis of ammonia and its derivatives, as well as facilitate the use of ammonia as a hydrogen carrier for renewable energy storage.

Switching on/off molybdenum nitride catalytic activity in ammonia synthesis through modulating metal-support interaction.

Modulating the interaction between Mo nanoparticles and their support is an elegant approach to finely tune the structural, physico-chemical, redox and electronic properties of the active site. In this work, a series of molybdenum nitride catalysts supported on TiO2, and SBA-15 has been prepared and fully characterized. The results of characterization confirmed the high dispersion of Mo and the formation of small molybdenum nanoparticles in both the 10-Mo-N/SBA-15 and 10-Mo-N/TiO2 catalysts. In this context, we have shown that the catalytic activity of Mo species was strongly impacted by the nature of the catalytic support. Amongst the studied supports, SBA-15 was found to be the most appropriate for Mo dispersion. In comparison, when supported on a reducible oxide (TiO2), Mo species showed poor catalytic activity in both ammonia synthesis and decomposition and were prone to quick deactivation in the ammonia synthesis reaction. Evidence of charge transfer from the reducible support to the active phase, indicative of possible SMSI behaviour, has been observed by XPS and EPR. Differences in the oxidation states, redox behaviours, and electronic properties have been further studied by means of EPR, H2-TPR and H2-TPD.

Milling-Assisted Loading of Drugs into Mesoporous Silica Carriers: A Green and Simple Method for Obtaining Tunable Customized Drug Delivery.

Mesoporous silica (MPS) carriers are considered as a promising strategy to increase the solubility of poorly soluble drugs and to stabilize the amorphous drug delivery system. The development by the authors of a solvent-free method (milling-assisted loading, MAL) made it possible to manipulate the physical state of the drug within the pores. The present study focuses on the effects of the milling intensity and the pore architecture (chemical surface) on the physical state of the confined drug and its release profile. Ibuprofen (IBP) and SBA-15 were used as the model drug and the MPS carrier, respectively. It was found that decreasing the milling intensity promotes nanocrystallization of confined IBP. Scanning electron microscopy and low-frequency Raman spectroscopy investigations converged into a bimodal description of the size distribution of particles, by decreasing the milling intensity. The chemical modification of the pore surface with 3-aminopropyltriethoxisylane also significantly promoted nanocrystallization, regardless of the milling intensity. Combined analyses of drug release profiles obtained on composites prepared from unmodified and modified SBA-15 with various milling intensities showed that the particle size of composites has the greatest influence on the drug release profile. Tuning drug concentration, milling intensity, and chemical surface make it possible to easily customize drug delivery.

Manipulating the physical states of confined ibuprofen in SBA-15 based drug delivery systems obtained by solid-state loading: Impact of the loading degree.

Using the Milling-Assisted Loading (MAL) solid-state method for loading a poorly water-soluble drug (ibuprofen, IBP) within the SBA-15 matrix has given the opportunity to manipulate the physical state of drugs for optimizing bioavailability. The MAL method makes it easy to control and analyze the influence of the degree of loading on the physical state of IBP inside the SBA-15 matrix with an average pore diameter of 9.4 nm. It was found that the density of IBP molecules in an average pore size has a direct influence on both the glass transition and the mechanism of crystallization. Detailed analyzes of the crystallite distribution and melting by Raman mapping, x-ray diffraction, and differential scanning calorimetry have shown that the crystals are localized in the core of the channel and surrounded by a liquid monolayer. The results of these complementary investigations have been used for determining the relevant parameters (related to the SBA-15 matrix and to the IBP molecule) and the nature of the physical state of the confined matter.

Mechanism and kinetics of catalytic ozonation for elimination of organic compounds with spinel-type CuAl2O4 and its precursor.

CuAl2O4 based mixed oxides were used as heterogeneous catalysts for ozone activation to degrade organics in aqueous solution. The solids were thoroughly characterized by SEM/EDS, N2 physisorption, XRD, FTIR, Pyridine-FTIR, TEM and XPS. We demonstrated that the solid precursor calcined at 300 °C exhibited the best catalytic ozonation activity with respect to CuAl2O4 spinel phase obtained at higher temperatures. Such performance was attributed to the better textural properties and a higher density of active sites (hydroxyl groups and Lewis acidity). Specifically, the mixed oxide/O3 process allows to reach a near complete color removal of the dye solution (100 mg L-1) in 25 min at neutral pH. Corresponding reaction rate value was measured at 0.112 min-1 and was clearly higher compared with the single oxide ozonation process (0.071 min-1 for CuO/O3 and 0.074 min-1 for Al2O3/O3). Then, we proposed that such catalytic performance was related to a synergistic function between ≡Cu2+ and ≡Al3+, which took part of a mechanism of radical formation. In such mechanism, present ≡Al3+ could act as a reservoir for surface active sites such as hydroxyl groups and Lewis acid sites, while ≡Cu2+ could provide the possibility of electron transfer with ozone for the enhancement of radical generation. We suggested that the interaction between chemisorbed ozone and surface hydroxyl groups initially stabilized on ≡Al3+ initiated the generation of reactive radical species. This interaction led as well to the formation of surface adsorbed HO and few O2- on ≡Cu2+ Lewis acid sites. Besides, the interfacial redox reaction with ozone is favored by the presence of ≡Cu2+ following the sequence of ≡Cu2+/≡Cu+/≡Cu2+ redox cycle.

ß-Keto-enol Tethered Pyridine and Thiophene: Synthesis, Crystal Structure Determination and Its Organic Immobilization on Silica for Efficient Solid-Liquid Extraction of Heavy Metals.

Molecules bearing ß-keto-enol functionality are potential candidates for coordination chemistry. Reported herein is the first synthesis and use of a novel designed ligand based on ß-keto-enol group embedded with pyridine and thiophene moieties. The product was prepared in a one-step procedure by mixed Claisen condensation and was characterized by EA, m/z, FT-IR, (¹H, (13)C) NMR and single-crystal X-ray diffraction analysis. The new structure was grafted onto silica particles to afford a chelating matrix which was well-characterized by EA, FT-IR, solid-state (13)C-NMR, BET, BJH, SEM and TGA. The newly prepared organic-inorganic material was used as an adsorbent for efficient solid-phase extraction (SPE) of Cu(II), Zn(II), Cd(II) and Pb(II) from aqueous solutions and showed a capture capacity of 104.12 mg·g(-1), 98.90 mg·g(-1), 72.02 mg·g(-1), and 65.54 mg·g(-1), respectively. The adsorption capacity was investigated, in a batch method, using time of contact, pH, initial concentration, kinetics (Langmuir and Freundlich models), and thermodynamic parameters (ΔG°, ΔH° and ΔS°) of the system effects.

Efficient and robust reforming catalyst in severe reaction conditions by nanoprecursor reduction in confined space.

The in situ autocombustion synthesis route is shown to be an easy and efficient way to produce nanoscaled nickel oxide containing lanthanum-doped mesoporous silica composite. Through this approach, ~3 nm NiO particles homogeneously dispersed in the pores of silica are obtained, while lanthanum is observed to cover the surface of the silica pore wall. Subsequent reduction of such composite precursors under hydrogen generates Ni(0) nanoparticles of a comparable size. Control over the size and size distribution of metallic nanoparticles clearly improved catalytic activity in the methane dry reforming reaction. In addition, these composite materials exhibit excellent stability under severe reaction conditions. This was achieved through the presence of LaOx species, which reduced active-site carbon poisoning, and the confinement effect of the mesoporous support, which reduced metallic particle sintering.

Enhanced solid-state NMR correlation spectroscopy of quadrupolar nuclei using dynamic nuclear polarization.

By means of a true sensitivity enhancement for a solid-state NMR spectroscopy (SSNMR) experiment performed under dynamic nuclear polarization (DNP) conditions, corresponding to 4-5 orders of magnitude of time savings compared with a conventional SSNMR experiment, it is shown that it is possible to record interface-selective (27)Al-(27)Al two-dimensional dipolar correlation spectra on mesoporous alumina, an advanced material with potential industrial applications. The low efficiency of cross-polarization and dipolar recoupling for quadrupolar nuclei is completely negated using this technique. The important presence of pentacoordinated Al has not only been observed, but its role in bridging interfacial tetra- and hexacoordinated Al has been determined. Such structural information, collected at low temperature (∼103 K) and 9.4 T with the use of DNP, would have been impossible to obtain under standard conditions, even using a higher magnetic field. However, here it is demonstrated that this information can be obtained in only 4 h. This work clearly opens a new avenue for the application of SSNMR to quadrupolar nuclei and notably the atomic-scale structure determination of catalysis materials such as mesoporous alumina.

A general route to synthesize supported isolated oxide and mixed-oxide nanoclusters at sizes below 5 nm.

A simple and efficient route to prepare supported nanocrystalline oxides is presented. The synthesis procedure, i.e. in situ autocombustion of a glycine complex, allows the production of nanocrystals in a porous matrix presenting larger pore size. An example of successful formation of 2-5 nm nanocrystals is given for a single oxide (Fe(2)O(3)), a mixed-oxide structure (LaCoO(3) perovskite-type) and a nickel-doped oxide.

An efficient route to highly organized, tunable macroporous-mesoporous alumina.

Organized macroporous-mesoporous alumina can be obtained via a dual-templating approach. Monodispersed polystyrene beads promote macropore formation, while a P123 surfactant templating agent drives the formation of ordered hexagonal mesopores throughout the alumina framework. These well-defined pore networks coexist over a wide range of temperatures and macropore sizes.