The Enhanced Catalytic Performance and Stability of Ordered Mesoporous Carbon Supported Nano-Gold with High Structural Integrity for Glycerol Oxidation.

Ordered mesoporous carbon (OMC) supported gold nanoparticles of size 3-4 nm having uniform dispersion were synthesized by sol-immobilization method. OMCs such as CMK-3 and NCCR-56 with high surface area and uniform pore size were obtained, respectively, using ordered mesoporous silicas such as SBA-15 and IITM-56 as hard templates, respectively. The resulting OMC supported monodispersed nano-gold, i. e., Au/CMK-3 and Au/NCCR-56, exhibited excellent performance as mild-oxidizing catalysts for oxidation of glycerol with high hydrothermal stability. Further, unlike activated carbon supported nano-gold catalysts (Au/AC), the OMC supported nano-gold catalysts, i. e., Au/CMK-3 and Au/NCCR-56, show no aggregation of active species even after recycling. Thus, in the case of Au/CMK-3 and Au/NCCR-56, both the fresh and regenerated catalysts showed excellent performane for the chosen reaction owing to an enhanced textural integrity of the catalysts and that with remarkable selectivity towards glyceric acid. The significance of the OMC supports in maintaining the dispersion of gold nanoparticles is explicit from this study, and that the activity of Au/AC catalyst is considerably decreased (∼50 %) upon recycling as a result of agglomeration of the active gold nanoparticles over the disordered amorphous carbon matrix.

Acid-Mediated Synthesis of Ordered Mesoporous Aluminosilicates: The Challenge and the Promise.

A new intrinsic hydrolysis method was employed, for the first-time, to synthesize well-ordered H-AlSBA-15 with trivalent aluminium exclusively in the tetrahedral framework structure of SBA-15. Unlike other methods, which involve incorporation of aluminium ions in both the framework (Brønsted) and non-framework (Lewis) sites of the silicate matrix, the intrinsic hydrolysis method isomorphously substitutes aluminium ions in the tetrahedral network even at high aluminium content. This unique approach relies mainly on the hydrolysis rates of the inorganic (silicon and aluminium) precursors used for the preparation in such a way that the condensation occurs simultaneously so as to overcome the usually encountered difficulties in stabilizing aluminium ions in the silicate matrix. In this way, we could successfully synthesize high quality Brønsted acidic H-AlSBA-15, hitherto not reported. The synthesized materials were systematically characterized by various analytical, spectroscopic, and imaging techniques, including XRD, Brunauer-Emmett-Teller (BET) surface area measurements, TEM, SEM, 29 Si and 27 Al magic angle spinning NMR spectroscopy, X-ray fluorescence (XRF), and NH3 temperature-programmed desorption (TPD). The characterization results reveal the presence of a highly porous structure (with narrow pores) and tetrahedrally coordinated trivalent aluminium in the silicate matrix with more medium to strong Brønsted acid sites. The resulting high quality catalysts exhibit excellent activity for tert-butylation of phenol with high selectivity towards para-tert-butyl phenol and 2,4-di-tert-butyl phenol.

Mesoporous γ-Iron Oxide Nanoparticles for Magnetically Triggered Release of Doxorubicin and Hyperthermia Treatment.

Mesoporous iron-oxide nanoparticles (mNPs) were prepared by using a modified nanocasting approach with mesoporous carbon as a hard template. mNPs were first loaded with doxorubicin (Dox), an anticancer drug, and then coated with the thermosensitive polymer Pluronic F108 to prevent the leakage of Dox molecules from the pores that would otherwise occur under physiological conditions. The Dox-loaded, Pluronic F108-coated system (Dox@F108-mNPs) was stable at room temperature and physiological pH and released its Dox cargo slowly under acidic conditions or in a sudden burst with magnetic heating. No significant toxicity was observed in vitro when Dox@F108-mNPs were incubated with noncancerous cells, a result consistent with the minimal internalization of the particles that occurs with normal cells. On the other hand, the drug-loaded particles significantly reduced the viability of cervical cancer cells (HeLa, IC50 =0.70 µm), wild-type ovarian cancer cells (A2780, IC50 =0.50 µm) and Dox-resistant ovarian cancer cells (A2780/AD, IC50 =0.53 µm). In addition, the treatment of HeLa cells with both Dox@F108-mNPs and subsequent alternating magnetic-field-induced hyperthermia was significantly more effective at reducing cell viability than either Dox or Dox@F108-mNP treatment alone. Thus, Dox@F108-mNPs constitute a novel soft/hard hybrid nanocarrier system that is highly stable under physiological conditions, temperature-responsive, and has chemo- and thermotherapeutic modes of action.

Crystal structure of bis-(acetato-κO)di-aqua-(2,2'-bi-pyridine-κ(2) N,N')manganese(II).

In the title monomeric manganese(II) complex, [Mn(CH3COO)2(C10H8N2)(H2O)2], the metal ion is coordinated by a bidentate 2,2'-bi-pyridine (bpy) ligand, two water mol-ecules and two axial acetate anions, resulting in a highly distorted octa-hedral environment. The aqua ligands are stabilized by the formation of strong intra-molecular hydrogen bonds with the uncoordinated acetate O atoms, giving rise to pseudo-bridging arrangement of the terminal acetate groups. In the crystal, the mol-ecules form [010] zigzag chains via O-H⋯O hydrogen bonds involving the aqua ligands and acetate O atoms. Further, the water and bpy ligands are trans to each other, and are arranged in an off-set fashion showing inter-molecular π-π stacking between nearly parallel bi-py rings, the centroid-centroid separations being 3.8147 (12) and 3.9305 (13) Å.

Ionic Liquid Templated Ordered Hexagonal Mesoporous Iron Phosphate Molecular Sieves: A Highly Effective Heterogeneous Catalysts with Remarkable Selectivity for Phenol Hydroxylation Reaction.

A highly organized hexagonal mesoporous iron phosphate framework structure with the designation HMI-41 was successfully synthesized for the first-time in a reproducible way using imidazolium-based ionic liquid as structure directing agent. The unique templating properties of ionic liquid generated a highly ordered well-crystallized mesoporous matrix having high surface area (445 m2 g-1 ), thicker pore wall (2.1 nm) and narrow pore size distribution (3.1 nm). The presence of active sites within a tetrahedral framework structure made the novel HMI-41 catalyst highly effective for phenol hydroxylation in an acidic medium with hydrogen peroxide as the oxidant. The catalyst exhibited outstanding performance, achieving an impressive 80% hydroquinone selectivity and 21% phenol conversion with a hydroquinone-to-catechol ratio of seven, which is the highest value ever reported.

Experimental and modelling studies of carbon dioxide capture onto pristine, nitrogen-doped, and activated ordered mesoporous carbons.

The search for suitable materials for carbon dioxide capture and storage has attracted the attention of the scientific community in view of the increased global CO2 levels and its after-effects. Among the different materials under research, porous carbons and their doped analogues are extensively debated for their ability to store carbon dioxide at high pressures. The present paper examined high-pressure carbon dioxide storage studies of 1-D hexagonal and 3-D cubic ordered mesoporous pristine and N-doped carbons prepared using the nano-casting method. Excess carbon dioxide sorption isotherms were obtained using the volumetric technique and were fitted using the Toth model. Various parameters that influence CO2 storage on metal-free ordered mesoporous carbons, such as the effect of pore size, pore dimension, pyrolysis temperature, the impact of nitrogen substitution, and the effect of ammonia activation are discussed. It was observed that the carbon dioxide storage capacity has an inverse relation to the total nitrogen doped, the amount of pyridinic nitrogen functionality, and the pyrolysis temperature, whereas the pore size seems to have a linear relationship. On the other hand, the presence of oxygen has a positive effect on the sorption capacity. Among the prepared ordered mesoporous carbons, the ammonia-treated one has shown the highest adsorption capacity of 37.8 mmol g-1 at 34 bar and 0 °C.

Electrochemical performance of nano-sized LiFePO4-embedded 3D-cubic ordered mesoporous carbon and nitrogenous carbon composites.

Herein, we report a single-step synthesis, characterization, and electrochemical performance of nano-sized LiFePO4 (LFP)-embedded 3D-cubic mesoporous carbon (CSI-809) and nitrogenous carbon (MNC-859) composites. Furthermore, in order to investigate the effects of both CSI-809 and MNC-859 on the electrochemical characteristics of LFP, a systematic study was performed on the morphology and microstructure of the composites, viz., LFP/CSI-809 and LFP/MNC-859, using XRD, FE-SEM, FT-Raman, and BET surface area analyses. Among these composites, LFP/MNC-859 exhibited better electrochemical performance with higher specific capacity and rate capability as compared to those of LFP/CSI-809. In addition, even after 100 cycles, LFP/MNC-859 retained 97% of its initial discharge capacity at 1C rate. The enhanced electrochemical performance of the nano-sized LFP-embedded MNC-859 can be attributed to the conductive nitrogenous carbon and mesoporosity, which facilitate electrolyte diffusion, and improved conductivity of the advanced LFP-nitrogenous porous carbon matrix.

Surfactant-Mediated and Morphology-Controlled Nanostructured LiFePO4/Carbon Composite as a Promising Cathode Material for Li-Ion Batteries.

The synthesis of morphology-controlled carbon-coated nanostructured LiFePO4 (LFP/Carbon) cathode materials by surfactant-assisted hydrothermal method using block copolymers is reported. The resulting nanocrystalline high surface area materials were coated with carbon and designated as LFP/C123 and LFP/C311. All the materials were systematically characterized by various analytical, spectroscopic and imaging techniques. The reverse structure of the surfactant Pluronic® 31R1 (PPO-PEO-PPO) in comparison to Pluronic® P123 (PEO-PPO-PEO) played a vital role in controlling the particle size and morphology which in turn ameliorate the electrochemical performance in terms of reversible specific capacity (163 mAh g-1 and 140 mAh g-1 at 0.1 C for LFP/C311 and LFP/C123, respectively). In addition, LFP/C311 demonstrated excellent electrochemical performance including lower charge transfer resistance (146.3 Ω) and excellent cycling stability (95 % capacity retention at 1 C after 100 cycles) and high rate capability (163.2 mAh g-1 at 0.1 C; 147.1 mAh g-1 at 1 C). The better performance of the former is attributed to LFP nanoparticles (<50 nm) with a specific spindle-shaped morphology. Further, we have also evaluated the electrode performance with the use of both PVDF and CMC binders employed for the electrode fabrication.

Nanoarchitectured peroxidase-mimetic nanozymes: mesoporous nanocrystalline α- or γ-iron oxide?

Nanozymes (nanoparticles with enzyme-like properties) have attracted considerable attention in recent years owing to their intrinsic enzyme-like properties and broad application in the fields of ELISA based immunoassay and biosensing. Herein, we systematically investigate the influence of crystal phases (γ-Fe2O3 and α-Fe2O3) of mesoporous iron oxide (IO) on their peroxidase mimetic activity. In addition, we have also demonstrated the applicability of these mesoporous IOs as nanozymes for detecting the glucose biomarker with a limit of detection (LOD) of 0.9 µM. Mesoporous γ-Fe2O3 shows high nanozyme activities (and magnetism) toward the catalytic oxidation of chromogenic substances, such as 3,3',5,5'-tetramethylbenzidine (TMB) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid)-ABTS, as well as for the colourimetric detection of glucose, compared to that of α-Fe2O3. We believe that this in-depth study of crystal structure based nanozyme activity will guide designing highly effective nanozymes based on iron oxide nanostructures for chemical sensing, biosensing and environmental remediation.

Rational design, synthesis, characterization and catalytic properties of high-quality low-silica hierarchical FAU- and LTA-type zeolites.

Despite the development of several synthetic strategies employing various templates as (pore) structure directing agents, the preparation of high-quality aluminum-rich hierarchical zeolites (designated as ZH) with Si/Al < 5 from its molecular precursors is still a challenge to the scientific community. For the first time, we report here, a successful synthesis methodology for the preparation of hierarchical zeolites, having FAU and LTA topologies with uniform micropores and mesopores by a rationally designed method. Here, a stable supramolecular self-assembly was achieved under the challenging synthesis conditions by tailoring the zeolitization process, viz., by a homogeneous nucleation and a multi-step crystallization. This has resulted in regular mesoporosity in FAU-type zeolites and a unique mesoporosity in LTA-type zeolites, hitherto not reported so far.

Designing ordered mesoporous aluminosilicates under acidic conditions via an intrinsic hydrolysis method.

Acid-mediated synthesis of ordered mesoporous aluminosilicates (OMAS) with medium-to-strong Brønsted acid sites and trivalent aluminium exclusively in a tetrahedral framework structure is realized by a newly devised intrinsic hydrolysis method. In this way, we have synthesized a series of well-ordered OMAS, e.g., H-AlSBA-15 and H-AlIITM-56, which are otherwise difficult to distinguish under acidic conditions owing to very different hydrolysis rates of both silicon and aluminium sources used for preparation as well as easy dissociation of thus formed Al-O-Si bonds. This novel intrinsic hydrolysis approach, however, relies mainly on similar hydrolysis rates of constituent inorganic species leading to efficient condensation. Thus, the innovative methodology using tetraethyl orthosilicate and aluminium citrate, respectively, as tetravalent silicon and trivalent aluminium as precursors facilitates the formation of high quality OMAS with a narrow pore size distribution, thicker walls, and trivalent aluminium in a tetrahedral framework structure with a high aluminium content, as evidenced by a battery of characterization techniques, viz., XRD, XRF, SEM, TEM and BET. The resulting materials, in turn, generate Brønsted acid sites in the aluminosilicate matrix, with the absence of the usually encountered Lewis acid sites, viz., extra-framework and/or non-framework species, as confirmed by both 27Al MAS-NMR and NH3-TPD studies. All the prepared catalysts exhibit excellent activity towards the tertiary butylation of phenol, and the high activity of the catalysts is attributed to the unique and exclusive presence of medium-to-strong acid sites in the OMAS matrix.

Transition-metal (Ti,V,Cr,Mn,Fe,Co,Cu) containing ordered nanoporous materials: novel heterogeneous catalysts for selective oxidation reactions.

Transition-metal (Ti,V,Cr,Mn,Fe,Co,Cu) containing periodic nanoporous catalysts, were synthesized hydrothermally and characterized using various analytical and spectroscopic techniques. The catalytic performance of the different catalysts was systematically evaluated with a detailed study on TiMCM-41. All the catalysts showed promise for the selective oxidation of cycloalkanes, viz., cyclohexane, cyclooctane, and cyclododecane, under mild reaction conditions. Furthermore, these mesoporous molecular sieves were also active for all the chosen reactions even after several recycling and/or washing treatments. Among the various materials under investigation, the catalysts TiMCM-41 and VMCM-41 showed much higher substrate conversion and excellent product selectivity in conjunction with a minimal leaching of the active species. More importantly, the influence of pore size on the catalytic activity of the bulkier substrates such as cyclooctane and cyclododecane is demonstrated.

Heterogeneous photocatalytic degradation of methanol over uranyl-anchored nanoporous MCM-41 and MCM-48.

The vapor-phase photodegradation of methanol to carbon dioxide was carried out over uranyl-anchored nanoporous MCM-41 and MCM-48 hosts (designated as UO2(2+)/MCM-41 and UO2(2+)/MCM-48, respectively) under simulated light and ambient conditions. Preliminary results indicate that the photoactivity of the latter is considerably decreased as compared to the former due to the presence of a smaller fraction of photoactive uranyl (UO2(2+)) ions in UO2(2+)/MCM-48.

Effect of the Titanium Nanoparticle on the Quantum Chemical Characterization of the Liquid Sodium Nanofluid.

Suspension state of a titanium nanoparticle in the liquid sodium was quantum chemically characterized by comparing physical characteristics, viz., electronic state, viscosity, and surface tension, with those of liquid sodium. The exterior titanium atoms on the topmost facet of the nanoparticle were found to constitute a stable Na-Ti layer, and the Brownian motion of a titanium nanoparticle could be seen in tandem with the surrounding sodium atoms. An electrochemical gradient due to the differences in electronegativity of both titanium and sodium causes electron flow from liquid sodium atoms to a titanium nanoparticle, Ti + Na → Ti(δ-) + Na(δ+), making the exothermic reaction possible. In other words, the titanium nanoparticle takes a role as electron-reservoir by withdrawing free electrons from sodium atoms and makes liquid sodium electropositive. The remaining electrons in the liquid sodium still make Na-Na bonds and become more stabilized. With increasing size of the titanium nanoparticle, the deeper electrostatic potential, the steeper electric field, and the larger Debye atmosphere are created in the electric double layer shell. Owing to electropositive sodium-to-sodium electrostatic repulsion between the external shells, naked titanium nanoparticles cannot approach each other, thus preventing the agglomeration.

Crystal structure of (2-formyl-phenolato-κ(2) O,O')oxido(2-{[(2-oxidoeth-yl)imino]-meth-yl}phenolato-κ(3) O,N,O')vanadium(V).

In the unsymmetrical title vanadyl complex, [V(C9H9NO2)(C7H5O2)O], one of the ligands (2-formyl-phenol) is disordered over two sets of sites, with an occupancy ratio of 0.55 (2):0.45 (2). The metal atom is hexa-coordinated, with a distorted octa-hedral geometry. The vanadyl O atom (which subtends the shortest V-O bond) occupies one of the apical positions and the remaining axial bond (the longest in the polyhedron) is provided by the (disordered) formyl O atoms. The basal plane is defined by the two phenoxide O atoms, the imino-alcoholic O and the imino N atom. The planes of the two benzene rings are almost perpendicular to each other, subtending an inter-planar angle of 84.1 (2)° between the major parts. The crystal structure features weak C-H⋯O and C-H⋯π inter-actions, forming a lateral arrangement of adjacent molecules.

Crystal structure of aquadioxido(2-{[(2-oxido-ethyl)-imino]-meth-yl}phenol-ato-κ(3) O,N,O')molybdenum(VI).

The mononuclear title complex, [Mo(C9H9NO2)O2(H2O)], contains an Mo(VI) atom in a distorted octa-hedral coordination sphere defined by an Mo=O and an Mo-(OH2) bond to the axial ligands and two Mo-O bonds to phenolate and alcoholate O atoms, another Mo=O bond and one Mo-N bond to the imino N atom in the equatorial plane. The five-membered metalla-ring shows an envelope conformation. In the crystal, individual mol-ecules are connected into a layered arrangement parallel to (100) by means of O-H⋯O hydrogen bonds involving the water mol-ecule as a donor group and the O atoms of neighbouring complexes as acceptor atoms. These inter-actions lead to the formation of a three-dimensional network.