Transition Metal-Promoted Carbon-Silicon Solid Acid Catalysts for the Synthesis and Process Optimization of Benzaldehyde Glycol Acetal.

A series of transition metal (M)-promoted carbon-silicon (C-M-Si; M=Mn, Fe, Co, Ni, Cu, Zn, Zr) solid acid catalysts with designated molar ratio of M/Si=1 : 8 were fabricated and exploited for acetalization of benzaldehyde (BzH) with ethylene glycol (EG). The physical and chemical properties of these C-M-Si catalysts prepared by sol-gel method were characterized by various techniques, namely, SEM, EDS, TGA-DTG, BET, XRD, FTIR, XPS, and NH3 -TPD. Among various examined acidic C-M-Si catalysts, the C-Fe-Si catalyst exhibited the optimal catalytic activity with the benzaldehyde glycol acetal (BEGA) yield of 97.67 %, in excellent agreement with the value (97.88 %) predicted by the response surface methodology (RSM) based on a Box-Behnken design (BBD). C-Fe-Si catalyst with the high catalytic activities and excellent stability and reusability may be ascribed to the suitable acidity and uniform surface distribution of active sites requisite for the acid-catalyzed acetalization reaction.

Molecular Understanding of the Catalytic Consequence of Ketene Intermediates under Confinement.

Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C-C bond coupling during the carbonylation reaction have been theoretically investigated under realistic reaction conditions and further validated by synchrotron radiation X-ray diffraction (SR-XRD) and Fourier transformed infrared (FT-IR) studies. It has been demonstrated that the zeolite confinement effect has significant influence on the formation, stability, and further transformation of ketene. Thus, the evolution and the role of reactive and inhibitive intermediates depend strongly on the framework structure and pore architecture of the zeolite catalysts. Inside side pockets of mordenite (MOR), rapid protonation of ketene occurs to form a metastable acylium ion exclusively, which is favorable toward methyl acetate (MA) and acetic acid (AcOH) formation. By contrast, in 12MR channels of MOR, a relatively longer lifetime was observed for ketene, which tends to accelerate deactivation of zeolite due to coke formation by the dimerization of ketene and further dissociation to diene and alkyne. Thus, we resolve, for the first time, a long-standing debate regarding the genuine role of ketene in zeolite catalysis. It is a paradigm to demonstrate the confinement effect on the formation, fate, and catalytic consequence of the active intermediates in zeolite catalysis.

31P NMR Chemical Shifts of Phosphorus Probes as Reliable and Practical Acidity Scales for Solid and Liquid Catalysts.

Acid-base catalytic reaction, either in heterogeneous or homogeneous systems, is one of the most important chemical reactions that has provoked a wide variety of industrial catalytic processes for production of chemicals and petrochemicals over the past few decades. In view of the fact that the catalytic performances (e.g., activity, selectivity, and reaction mechanism) of acid-catalyzed reactions over acidic catalysts are mostly dictated by detailed acidic features, viz. type (Brønsted vs Lewis acidity), amount (concentration), strength, and local environments (location) of acid sites, information on and manipulation of their structure-activity correlation are crucial for optimization of catalytic performances as well as innovative design of novel effective catalysts. This review aims to summarize recent developments on acidity characterization of solid and liquid catalysts by means of experimental 31P nuclear magnetic resonance (NMR) spectroscopy using phosphorus probe molecules such as trialkylphosphine (TMP) and trialkylphosphine oxides (R3PO). In particular, correlations between the observed 31P chemical shifts (δ31P) of phosphorus (P)-containing probes and acidic strengths have been established in conjuction with density functional theory (DFT) calculations, rendering practical and reliable acidity scales for Brønsted and Lewis acidities at the atomic level. As illustrated for a variety of different solid and liquid acid systems, such as microporous zeolites, mesoporous molecular sieves, and metal oxides, the 31P NMR probe approaches were shown to provide important acid features of various catalysts, surpassing most conventional methods such as titration, pH measurement, Hammett acidity function, and some other commonly used physicochemical techniques, such as calorimetry, temperature-programmed desorption of ammonia (NH3-TPD), Fourier transformed infrared (FT-IR), and 1H NMR spectroscopies.

Porous carbon-NiO nanocomposites for amperometric detection of hydrazine and hydrogen peroxide.

A hydrothermal route is reported for the preparation of a composite consisting of sheet-like glucose-derived carbon and nickel oxide nanoparticles. The nanocomposites were prepared at different annealing temperatures and exploited as electrode materials for amperometric (i-t) determination of hydrazine (N2H4) and hydrogen peroxide (H2O2) at trace levels. The performances of the sensors were assessed by cyclic voltammetry and amperometry detection using a rotating disk electrode (RDE) technique. The modified electrode annealed at ca. 300 °C was found to exhibit the best electrocatalytic performance in terms of sensitive and selective detection of N2H4 and H2O2 even in the presence of interfering species. The electrode is inexpensive, robust, easy to prepare in large batches, highly stable, and has a low overpotential. H2O2 can be sensed, best at a working voltage of typically 0.13 V vs Ag/AgCl; rotationg speed 1200 rpm) over a wide concentration range (0.01 to 3.9 µM) with a detection limit of 1.5 nM. N2H4 can be sensed, best at a working voltage of typically 0.0 V within the concentration range from 0.5 µM to 12 mM with an excellent detection limit of 1.5 µM. Thus, this cost-effective and robust modified electrode, which may be readily prepared in large batch quantity, represents a practical platform for industrial sensing. Graphical abstract Schematic of the hydrothermal method for synthesis of carbon and nickel oxide nanoparticle composites (GCD/NiO-150, GCD/NiO-300, and GCD/NiO-450). The composite was used for the electro-oxidation of hydrazine (N2H4) and hydrogen peroxide (H2O2) by cyclic voltammetry and amperometry (i-t).

Origin and Structural Characteristics of Tri-coordinated Extra-framework Aluminum Species in Dealuminated Zeolites.

Post-synthetic dealumination treatment is a common tactic adopted to improve the catalytic performance of industrialized zeolitic catalysts through enhancements in acidity and stability. However, among the possible extra-framework aluminum (EFAL) species in dealuminated zeolites such as Al3+, Al(OH)2+, Al(OH)2+, AlO+, AlOOH, and Al(OH)3, the presence of tri-coordinated EFAL-Al3+ species, which exhibit large quadrupolar effect due to the lack of hydrogen-bonding species, was normally undetectable by conventional one- and two-dimensional 1H and/or 27Al solid-state nuclear magnetic resonance (SSNMR) techniques. By combining density functional theory (DFT) calculations with experimental 31P SSNMR using trimethylphosphine (TMP) as the probe molecule, we report herein a comprehensive study to certify the origin, fine structure, and possible location of tri-coordinated EFAL-Al3+ species in dealuminated HY zeolite. The spatial proximities and synergies between the Brønsted and various Lewis acid sites were clearly identified, and the origin for the observed EFAL-Al3+ species with ultra-strong Lewis acidity was deduced to be at the expense of adjacent Brønsted acid sites. The excellent performance of such tri-coordinated EFAL species was furthermore confirmed by glucose isomerization reactions.

Acidic Properties and Structure-Activity Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy.

Solid acid materials with tunable structural and acidic properties are promising heterogeneous catalysts for manipulating and/or emulating the activity and selectivity of industrially important catalytic reactions. On the other hand, the performances of acid-catalyzed reactions are mostly dictated by the acidic features, namely, type (Brønsted vs Lewis acidity), amount, strength, and local environment of acid sites. The latter is relevant to their location (intra- vs extracrystalline), and possible confinement and Brønsted-Lewis acid synergy effects that may strongly affect the host-guest interactions, reaction mechanism, and shape selectivity of the catalytic system. This account aims to highlight some important applications of state-of-the-art solid-state NMR (SSNMR) techniques for exploring the structural and acidic properties of solid acid catalysts as well as their catalytic performances and relevant reaction pathway invoked. In addition, density functional theory (DFT) calculations may be exploited in conjunction with experimental SSNMR studies to verify the structure-activity correlations of the catalytic system at a microscopic scale. We describe in this Account the developments and applications of advanced ex situ and/or in situ SSNMR techniques, such as two-dimensional (2D) double-quantum magic-angle spinning (DQ MAS) homonuclear correlation spectroscopy for structural investigation of solid acids as well as study of their acidic properties. Moreover, the energies and electronic structures of the catalysts and detailed catalytic reaction processes, including the identification of reaction species, elucidation of reaction mechanism, and verification of structure-activity correlations, made available by DFT theoretical calculations were also discussed. Relevant discussions will focus primarily on results obtained from our laboratories in the past decade, including (i) quantitative and qualitative acidity characterization utilizing assorted probe molecules, (ii) probing the spatial proximity and synergy effect of acid sites, and (iii) influence of acid features and pore confinement effect on catalytic activity, transition-state stability, reaction pathway, and product selectivity of solid acid catalysts such as zeolites, metal oxides, and heteropolyacids. It is conclusive that a synergy of acidity (local effect) and pore confinement (environmental effect) tend to strongly dictate the formations of intermediates and transition states, hence, the reaction pathways and catalytic performance of solid acid catalysts. We hope that these information can provide additional insights toward our understanding in heterogeneous catalysis, especially the roles of structural and acidic properties on catalytic performances and reaction mechanism of acid-catalyzed systems, which should be beneficial for rational design of solid acid catalysts.

Functional porous carbon-ZnO nanocomposites for high-performance biosensors and energy storage applications.

A one-pot synthesis method for the fabrication of biomass-derived activated carbon-zinc oxide (ZAC) nanocomposites using sugarcane bagasse as a carbon precursor and ZnCl2 as an activating agent is reported. For the first time, we used ZnCl2 as not only an activating agent and also for the synthesis of ZnO nanoparticles on the AC surface. ZAC materials with varying ZnO loading were prepared and characterized by a variety of analytical and spectroscopic techniques such as FE-SEM, FE-TEM, XRD, EA, XPS, and Raman spectroscopy. ZAC-modified glassy carbon electrodes (GCEs) were found to exhibit remarkable electrochemical properties for simultaneous detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) as well as hazardous pollutants such as hydrogen peroxide (H2O2) and hydrazine (N2H4) with desirable sensitivity, selectivity, and detection limits. Moreover, ZAC-modified stainless steel electrodes also showed superior performances for supercapacitor applications. The ZAC nanocomposites, which may be mass produced by the reported facile direct route from sugarcane bagasse, are not only eco-friendly but also cost-effective, and thus, are suitable as a practical platform for bio-sensing and energy storage applications.

Functional porous carbon/nickel oxide nanocomposites as binder-free electrodes for supercapacitors.

High-surface-area, guava-leaf-derived, heteroatom-containing activated carbon (GHAC) materials were synthesized by means of a facile chemical activation method with KOH as activating agent and exploited as catalyst supports to disperse nickel oxide (NiO) nanocrystals (average size (2.0±0.1) nm) through a hydrothermal process. The textural and structural properties of these GHAC/NiO nanocomposites were characterized by various physicochemical techniques, namely, field-emission SEM, high-resolution TEM, elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy. The as-synthesized GHAC/NiO nanocomposites were employed as binder-free electrodes, which exhibited high specific capacitance (up to 461 F g(-1) at a current density of 2.3 A g(-1)) and remarkable cycling stability, which may be attributed to the unique properties of GHAC and excellent electrochemical activity of the highly dispersed NiO nanocrystals.

Porous carbon-modified electrodes as highly selective and sensitive sensors for detection of dopamine.

Carbon porous materials (CPMs) with high surface areas up to 2660 m(2) g(-1), directly fabricated by a facile microwave-assisted route, were applied to the electrochemical detection of dopamine (DA). The CPM-modified electrodes exhibited excellent selectivity, a desirable detection limit (2.9 nM), and extraordinary sensitivity (2.56 mA µM(-1) cm(-2)) for detection of DA, even in the presence of large amounts of foreign species, such as ascorbic acid (AA) and uric acid (UA), making feasible the practical applications of these electrodes as DA sensors.

Understanding the high photocatalytic activity of (B, Ag)-codoped TiO2 under solar-light irradiation with XPS, solid-state NMR, and DFT calculations.

The origin of the exceptionally high activity of (B, Ag)-codoped TiO(2) catalysts under solar-light irradiation has been investigated by XPS and (11)B solid-state NMR spectroscopy in conjunction with density functional theory (DFT) calculations. XPS experimental results demonstrated that a portion of the dopant Ag (Ag(3+)) ions were implanted into the crystalline lattice of (B, Ag)-codoped TiO(2) and were in close proximity to the interstitial B (B(int.)) sites, forming [B(int.)-O-Ag] structural units. In situ XPS experiments were employed to follow the evolution of the chemical states of the B and Ag dopants during UV-vis irradiation. It was found that the [B(int.)-O-Ag] units could trap the photoinduced electron to form a unique intermediate structure in the (B, Ag)-codoped TiO(2) during the irradiation, which is responsible for the photoinduced shifts of the B 1s and Ag 3d peaks observed in the in situ XPS spectra. Solid-state NMR experiments including (11)B triple-quantum and double-quantum magic angle spinning (MAS) NMR revealed that up to six different boron species were present in the catalysts and only the tricoordinated interstitial boron (T*) species was in close proximity to the substitutional Ag species, leading to formation of [T*-O-Ag] structural units. Furthermore, as demonstrated by DFT calculations, the [T*-O-Ag] structural units were responsible for trapping the photoinduced electrons, which prolongs the life of the photoinduced charge carriers and eventually leads to a remarkable enhancement in the photocatalytic activity. All these unprecedented findings are expected to be crucial for understanding the roles of B and Ag dopants and their synergistic effect in numerous titania-mediated photocatalytic reactions.

Acidity characterization of heterogeneous catalysts by solid-state NMR spectroscopy using probe molecules.

Characterization of the surface acidic properties of solid acid catalysts is a key issue in heterogeneous catalysis. Important acid features of solid acids, such as their type (Brønsted vs. Lewis acid), distribution and accessibility (internal vs. external sites), concentration (amount), and strength of acid sites are crucial factors dictating their reactivity and selectivity. This short review provides information on different solid-state NMR techniques used for acidity characterization of solid acid catalysts. In particular, different approaches using probe molecules containing a specific nucleus of interest, such as pyridine-d5, 2-(13)C-acetone, trimethylphosphine, and trimethylphosphine oxide, are compared. Incorporation of valuable information (such as the adsorption structure, deprotonation energy, and NMR parameters) from density functional theory (DFT) calculations can yield explicit correlations between the chemical shift of adsorbed probe molecules and the intrinsic acid strength of solid acids. Methods that combine experimental NMR data with DFT calculations can therefore provide both qualitative and quantitative information on acid sites.

Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules.

A brief review is presented on acidity characterization of solid acid catalysts by means of solid-state phosphor-31 magic-angle-spinning nuclear magnetic resonance ((31)P MAS NMR) spectroscopy using phosphor-containing molecules as probes. It is emphasized that such a simple approach using (31)P MAS NMR of adsorbed phosphorous probe molecules, namely trimethylphosphine (TMP) and trialkylphosphine oxides (R(3)PO), represents a unique technique in providing detailed qualitative and quantitative features, viz. type, strength, distribution, and concentration of acid sites in solid acid catalysts. In particular, it will be shown that when applied with a proper choice of probe molecules with varied sizes and results obtained from elemental analysis, the amounts and locations (intracrystalline vs. extracrystalline) of different types (Brønsted vs. Lewis) of acid sites may be determined. In addition, by incorporating the NMR results with that obtained from theoretical density functional theory (DFT) calculations, correlations between the (31)P chemical shifts (δ(31)P) and acidic strengths of Brønsted and Lewis acid sites may also be derived, facilitating a suitable acidity scale for solid acid catalysts.

Prefabricated 3D-Printed Tissue-Engineered Bone for Mandibular Reconstruction: A Preclinical Translational Study in Primate.

The advent of three dimensionally (3D) printed customized bone grafts using different biomaterials has enabled repairs of complex bone defects in various in vivo models. However, studies related to their clinical translations are truly limited. Herein, 3D printed poly(lactic-co-glycolic acid)/ß-tricalcium phosphate (PLGA/TCP) and TCP scaffolds with or without recombinant bone morphogenetic protein -2 (rhBMP-2) coating were utilized to repair primate's large-volume mandibular defects and compared efficacy of prefabricated tissue-engineered bone (PTEB) over direct implantation (without prefabrication). 18F-FDG PET/CT was explored for real-time monitoring of bone regeneration and vascularization. After 3-month's prefabrication, the original 3D-architecture of the PLGA/TCP-BMP scaffold was found to be completely lost, while it was properly maintained in TCP-BMP scaffolds. Besides, there was a remarkable decrease in the PLGA/TCP-BMP scaffold density and increase in TCP-BMP scaffolds density during ectopic (within latissimus dorsi muscle) and orthotopic (within mandibular defect) implantation, indicating regular bone formation with TCP-BMP scaffolds. Notably, PTEB based on TCP-BMP scaffold was successfully fabricated with pronounced effects on bone regeneration and vascularization based on radiographic, 18F-FDG PET/CT, and histological evaluation, suggesting a promising approach toward clinical translation.

Solid-state 31P NMR mapping of active centers and relevant spatial correlations in solid acid catalysts.

Solid acid catalysts are used extensively in various advanced chemical and petrochemical processes. Their catalytic performance (namely, activity, selectivity, and reaction pathway) mostly depends on their acid properties, such as type (Brønsted versus Lewis), location, concentration, and strength, as well as the spatial correlations of their acid sites. Among the diverse methods available for acidity characterization, solid-state nuclear magnetic resonance (SSNMR) techniques have been recognized as the most valuable and reliable tool, especially in conjunction with suitable probe molecules that possess observable nuclei with desirable properties. Taking 31P probe molecules as an example, both trimethylphosphine (TMP) and trimethylphosphine oxide (TMPO) adsorb preferentially to the acid sites on solid catalysts and thus are capable of providing qualitative and quantitative information for both Brønsted and Lewis acid sites. This protocol describes procedures for (i) the pretreatment of typical solid acid catalysts, (ii) adoption and adsorption of various 31P probe molecules, (iii) considerations for one- and two-dimensional (1D and 2D, respectively) NMR acquisition, (iv) relevant data analysis and spectral assignment, and (v) methodology for NMR mapping with the assistance of theoretical calculations. Users familiar with SSNMR experiments can complete 31P-1H heteronuclear correlation (HETCOR), 31P-31P proton-driven spin diffusion (PDSD), and double-quantum (DQ) homonuclear correlation with this protocol within 2-3 d, depending on the complexity and the accessible acid sites of the solid acid samples.

(13)C shielding tensors of crystalline amino acids and peptides: Theoretical predictions based on periodic structure models.

Precise theoretical predictions of NMR parameters are helpful for the spectroscopic identification of complicated biological molecules, especially for the carbon shielding tensors in amino acids. The (13)C shielding tensors of various crystalline amino acids and peptides have been calculated using the gauge-including projector augmented wave (GIPAW) method based on two different periodic structure models, namely that deduced from available crystallographic data and that from theoretically optimized structures. The incorporation of surrounding lattice effects is found to be crucial in obtaining reliable predictions of (13)C shielding tensors that are comparable to the experimental data. This is accomplished by refining the experimental crystallographic data of the amino acids and peptides at the GGA/PBE level by which more accurate intramolecular C--H bond lengths and intermolecular hydrogen-bonding interactions are obtained. Accordingly, more accurate predictions of (13)C shielding tensors comparable to the experimental results (within a maximum deviation of +/-10 ppm) were achieved, rendering more explicit (13)C shielding tensors assignments for solid biological systems particularly for amino acids with multiple carboxyl carbons, such as asparagine, glutamine, and glutamic acid.

Heteronuclear dipolar recoupling of half-integer quadrupole nuclei under fast magic angle spinning.

An experimental method for the heteronuclear dipolar recoupling of half-integer quadrupole nuclei is proposed. The idea is to manipulate the central transition based on the recoupling technique of spin-polarization-inversion rotary resonance. This method allows the extraction of structural parameters under fast magic-angle spinning. Its validity has been examined by the average Hamiltonian theory and numerical simulations. The initial rotational-echo dephasing arising from the dipolar evolution can be approximated by a parabolic function, from which the heteronuclear van Vleck second moment can be estimated. A factor, estimated from two-spin simulations, is required to account for the effects of the quadrupolar coupling and is rather independent of the geometry and the orders of the spin systems. Our method can facilitate the structural characterization of materials containing half-integer quadrupole nuclei under high-resolution condition. Experimental verification has been carried out on two aluminophosphate systems, namely, AlPO(4)-5 and AlPO(4)-11.

Theoretical predictions of 31p NMR chemical shift threshold of trimethylphosphine oxide absorbed on solid acid catalysts.

The 31P NMR chemical shifts of adsorbed trimethylphosphine oxide (TMPO) and the configurations of the corresponding TMPOH+ complexes on Brønsted acid sites with varying acid strengths in modeled zeolites have been predicted theoretically by means of density functional theory (DFT) quantum chemical calculations. The configuration of each TMPOH+ complex was optimized at the PW91/DNP level based on an 8T cluster model, whereas the 31P chemical shifts were calculated with the gauge including atomic orbital (GIAO) approach at both the HF/TZVP and MP2/TZVP levels. A linear correlation between the 31P chemical shift of adsorbed TMPO and the proton affinity of the solid acids was observed, and a threshold for superacidity (86 ppm) was determined. This threshold for superacidity was also confirmed by comparative investigations on other superacid systems, such as carborane acid and heteropolyoxometalate H3PW12O40. In conjunction with the strong correlation between the MP2 and the HF 31P isotropic shifts, the 8T cluster model was extended to more sophisticated models (up to 72T) that are not readily tractable at the GIAO-MP2 level, and a 31P chemical shift of 86 ppm was determined for TMPO adsorbed on zeolite H-ZSM-5, which is in good agreement with the NMR experimental data.

31P chemical shift of adsorbed trialkylphosphine oxides for acidity characterization of solid acids catalysts.

A comprehensive study has been made to predict the adsorption structures and (31)P NMR chemical shifts of various trialkylphosphine oxides (R3PO) probe molecules, viz., trimethylphosphine oxide (TMPO), triethylphosphine oxide (TEPO), tributylphosphine oxide (TBPO), and trioctylphosphine oxide (TOPO), by density functional theory (DFT) calculations based on 8T zeolite cluster models with varied Si-H bond lengths. A linear correlation between the (31)P chemical shifts and proton affinity (PA) was observed for each of the homologous R3PO probe molecules examined. It is found that the differences in (31)P chemical shifts of the R3POH(+) adsorption complexes, when referring to the corresponding chemical shifts in their crystalline phase, may be used not only in identifying Brønsted acid sites with varied acid strengths but also in correlating the (31)P NMR data obtained from various R3PO probes. Such a chemical shift difference therefore can serve as a quantitative measure during acidity characterization of solid acid catalysts when utilizing (31)P NMR of various adsorbed R3PO, as proposed in our earlier report (Zhao; et al. J. Phys. Chem. B 2002, 106, 4462) and also illustrated herein by using a mesoporous H-MCM-41 aluminosilicate (Si/Al = 25) test adsorbent. It is indicative that, with the exception of (TMPO), variations in the alkyl chain length of the R3PO (R = C(n)H(2n+1); n > or = 2) probe molecules have only negligible effect on the (31)P chemical shifts (within experimental error of ca. 1-2 ppm) either in their crystalline bulk or in their corresponding R3POH(+) adsorption complexes. Consequently, an average offset of 8 +/- 2 ppm was observed for (31)P chemical shifts of adsorbed R3PO with n > or = 2 relative to TMPO (n = 1). Moreover, by taking the value of 86 ppm predicted for TMPO adsorbed on 8T cluster models as a threshold for superacidity (Zheng; et al. J. Phys. Chem. B 2008, 112, 4496), a similar threshold (31)P chemical shift of ca. 92-94 ppm was deduced for TEPO, TBPO, and TOPO.

Characterization of nanoporous structures of polyphenylene oxide derived carbon membranes by means of 129Xe NMR.

The 129Xe NMR spectroscopy has become a powerful technique of materials characterization because the xenon atom has a very large polarizability. It is well known that the signal of xenon sorbed in porous media is sensitively affected by the surrounding environments such as the chemistry of material surface. In this study, the pore properties of nanoporous PPO (polyphenylene oxide) derived carbon membranes were characterized by means of the variable temperature (VT)-hyperpolarized Xe NMR. The Xe NMR results showed good agreements with the adsorption results of CO2 for the PPO derived nanoporous carbon membranes. It was clearly shown that the 129Xe NMR could be used as one of the promising characterization methods of nanoporous materials with low surface area and small pore volume.

Well-dispersed rhenium nanoparticles on three-dimensional carbon nanostructures: Efficient catalysts for the reduction of aromatic nitro compounds.

Rhenium nanoparticles (ReNPs) supported on ordered mesoporous carbon (OMC) as a catalyst (Re/OMC) through a solvent-evaporation induced self-assembly (ELSA) method were prepared. The synthesized heterogonous catalyst was fully characterized using X-ray diffraction, field emission transmission electron microscopy, N2 sorption, metal dispersion, thermogravimetric analysis, Raman, Fourier-transform infrared, and X-ray photon spectroscopies. In addition, the catalyst was applied to reduce the aromatic nitro compounds (ANCs) for the first time in aqueous media and the reactions were monitored by following the intensity changes in the UV-vis absorption spectra with respect to time. This method provides the advantages of obtaining a high rate constant (k), green reaction conditions, simple methodology, easy separation and easy workup procedures. Moreover, the catalyst can be easily recovered by centrifugation, recycled several times and reused without any loss of activity. The higher activity of this catalyst was attributed to higher dispersion and smaller particle size of ReNPs as observed from FE-TEM and XRD results.