In situ NMR spectroscopy in heterogeneous catalysis: Kinetic study of hydrocarbon conversion mechanisms

The potential of high-resolution solid-state NMR spectroscopy for kinetic and mechanistic studies of hydrocarbon conversion on solid acid catalysis between 20 and 300°C is considered. The use of this technique is illustrated by the elucidation of the mechanisms of hydrogen exchange and ¹³C label transfer in alkanes and olefins, n-butane isomerization on sulfated zirconia, and ethane aromatization on zinc-containing zeolite beta. The kinetic parameters determined in these studies provide a basis for quantum chemical calculations of possible hydrocarbon activation and conversion pathways and for evaluating the reliability and accuracy of these theoretical calculations.     

The theoretical approach to surface chemistry and heterogeneous catalysis

Transition metals are the most interesting items among heavy atoms due to their extensive use in catalysis. Present understanding of heterogeneous catalytic reactions is still very poor, and new experimental and theoretical techniques have been developed in recent years with the aim of elucidating the mechanism of adsorption and reaction of simple molecules over metal surfaces or clusters. Empirical, semiempirical, and ab initio methods of calculations are briefly reviewed: results and perspectives are presented.     

In situ electron paramagnetic resonance: a unique tool for analyzing structure-reactivity relationships in heterogeneous catalysis

Electron Paramagnetic Resonance (EPR) offers widespread opportunities for monitoring catalytically relevant species that contain unpaired electrons under conditions close to those of heterogeneous catalytic gas and liquid phase reactions. In this tutorial review, after introducing basic theoretical and experimental principles of the technique, selected examples of typical applications are discussed that comprise (1) transition metal ions in paramagnetic valence states such as vanadium, (2) radical anions such as O˙(-) formed on oxide surfaces and (3) electrons in ferromagnetic particles such as nickel as well as in conduction bands of organic conductors such as polyaniline.     

Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy

This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.     

Chemo-regioselectivity in heterogeneous catalysis: competitive routes for C = O and C = C hydrogenations from a theoretical approach

The usual empirical rule stating that the C=C bond is more reactive than the C=O group for catalytic hydrogenations of unsaturated aldehydes is invalidated from the present study. Density functional theory calculations of all the competitive hydrogenation routes of acrolein on Pt(111) reveals conversely that the attack at the C=O bond is systematically favored. The explanation of such catalytic behavior is the existence of metastable precursor states for the O-H bond formation showing that the attack at the oxygen atom follows a new preferential mechanism where the C=O moiety is not directly bonded with the Pt surface atoms, hence yielding an intermediate pathway between Langmuir-Hinshelwood and Rideal-Eley general types of mechanisms. When the whole catalytic cycle is considered, our results reconcile with experimental studies devoted to hydrogenation of acrolein on Pt, since the desorption step of the partially hydrogenated product (unsaturated alcohol versus saturated aldehyde) plays a key role for the selectivity.     

Recent development in in situ NMR study on heterogeneous catalysis: mechanisms of light alkane functionalisation

In situ NMR studies of C(1)-C(5) light alkane activation and functionalisation in heterogeneous catalytic systems are overviewed. The results obtained from the NMR technique, particularly those quantitative ones, provide unique information on the activation of alkane molecules and the nature of relevant intermediates, leading to better understanding reaction mechanisms and designing catalysts.     

Reference molecules for nonlinear optics: a joint experimental and theoretical investigation

Hyper-Rayleigh scattering (HRS) experiments and quantum chemical calculations are combined to investigate the second-order nonlinear optical responses of a series of reference molecules, namely, carbon tetrachloride, chloroform, trichloroacetonitrile, acetonitrile, and dichloromethane. The multipolar decomposition of the first hyperpolarizability tensor through the use of the spherical harmonics formalism is employed to highlight the impact of the symmetry of the molecular scatterers on their nonlinear optical responses. It is demonstrated that HRS is a technique of choice to probe the molecular symmetry of the compounds. Coupled-cluster calculations performed at the coupled-cluster level with singles, doubles, and perturbative triples in combination with highly extended basis sets and including environment effects by using the polarizable continuum model qualitatively reproduce the molecular first hyperpolarizabilities and depolarization ratios of the molecular scatterers.     

Magnetic resonance imaging methods for in situ studies in heterogeneous catalysis

Magnetic resonance imaging (MRI) is a very powerful instrument used extensively in modern medical diagnostics because of its ability to look inside a body in a non-invasive and non-destructive way. Furthermore, MRI is more than just a single tool for extracting structural information. It is more of a sophisticated and versatile toolkit able to provide all sorts of useful information about the internal properties of an object under study and various processes within it, including heat and mass transport, composition and chemical transformations, in a spatially resolved mode. While a living body is different from a catalyst body or a reactor, the in situ and Operando studies in catalysis can clearly benefit from the use of this non-destructive toolkit as a powerful complement to other available spectroscopic tools. This tutorial review gives an introduction to the field and describes the examples of the applications of MRI to the studies of the preparation, deactivation and regeneration of solid catalysts and to the spectroscopy, thermometry and imaging studies of heterogeneous catalysts and model catalytic reactors performed during actual catalytic processes.     

In situ structural characterization of a recombinant protein in native Escherichia coli membranes with solid-state magic-angle-spinning NMR

The feasibility of using solid-state magic-angle-spinning NMR spectroscopy for in situ structural characterization of the LR11 (sorLA) transmembrane domain (TM) in native Escherichia coli membranes is presented. LR11 interacts with the human amyloid precursor protein (APP), a central player in the pathology of Alzheimer's disease. The background signals from E. coli lipids and membrane proteins had only minor effects on the LR11 TM resonances. Approximately 50% of the LR11 TM residues were assigned by using (13)C PARIS data. These assignments allowed comparisons of the secondary structure of the LR11 TM in native membrane environments and commonly used membrane mimics (e.g., micelles). In situ spectroscopy bypasses several obstacles in the preparation of membrane proteins for structural analysis and offers the opportunity to investigate how membrane heterogeneity, bilayer asymmetry, chemical gradients, and macromolecular crowding affect the protein structure.     

Infrared spectroscopy of copper-resveratrol complexes: a joint experimental and theoretical study

Infrared multiple-photon dissociation spectroscopy has been used to record vibrational spectra of charged copper-resveratrol complexes in the 3500-3700 cm(-1) and 1100-1900 cm(-1) regions. Minimum energy structures have been determined by density functional theory calculations using plane waves and pseudopotentials. In particular, the copper(I)-resveratrol complex presents a tetra-coordinated metal bound with two carbon atoms of the alkenyl moiety and two closest carbons of the adjoining resorcinol ring. For these geometries vibrational spectra have been calculated by using linear response theory. The good agreement between experimental and calculated IR spectra for the selected species confirms the overall reliability of the proposed geometries.     

In situ monitoring of solid-state polymerization reactions in sodium chloroacetate and sodium bromoacetate by 23Na and 13C solid-state NMR spectroscopy

The thermally induced solidstate polymerization reactions in sodium chloroacetate and sodium bromoacetate, leading to poly(hydroxyacetic acid) (polyglycolide) and NaCl and NaBr, respectively, were studied by isothermal in situ solid-state NMR spectroscopy at 120, 130 and 140 degrees C with a time resolution of the order of 5 to 25 min. The nuclei probed were 23Na and 13C, allowing the parent compounds (sodium halogenoacetates) and both reaction products (polymer and alkali halide) to be monitored. For sodium chloroacetate, there is no evidence for the involvement of intermediate phases during the reaction whereas this cannot be excluded for sodium bromoacetate. The crystal structure of sodium bromoacetate was determined directly from powder diffraction data by the Monte Carlo method, and was found to be isostructural with sodium chloroacetate. The topochemical reaction mechanism proposed previously for sodium chloroacetate is thus also applicable for the polymerization reaction in sodium bromoacetate. The mechanistic and kinetic information obtained from our in situ solid-state NMR investigations is compared and contrasted with information obtained from other in situ probes of the polymerization reactions in these materials.     

Analysis of a cycloheptenone derivative: an experimental and theoretical approach

A detailed analysis with total assignment of (1)H and (13)C NMR spectral data for a cycloheptenone derivative, a key intermediate for the synthesis of perhydroazulene terpenoids, is related. These assignments are based on 1D (1)H and (13)C NMR and on 2D NMR techniques including gCOSY, gHSQC, gHMBC, J-resolved and NOEDIF experiments. The unequivocal assignments were supported by theoretical chemical shifts and scalar coupling constant calculations at GIAO B3LYP/cc-pVDZ level from optimized structures at the same level of theory.     

"Single sample concept": theoretical model for a combinatorial approach to solid-state inorganic materials

A theoretical model for a "single sample concept" (SSC) applied to the combinatorial chemistry of solid-state inorganic compounds is presented. The SSC is performed by reacting N starting materials (randomly mixed) in a single sample of approximately 1 cm(3). Combinatorial calculations demonstrate that the number of reasonably estimated phases to be found in the space of N components grouped into compounds (e.g. oxides, sulfides, or halogenides) containing up to q < or = 6 metallic elements is smaller than combinations set up by starting conditions for local reactions within the bulk of a single ceramic sample. Recently, the SSC proved to work in the case of synthesizing libraries of 3d metal oxides, from which magnetic particulate matter was extracted by a magnetic separation technique. The SSC may be applied in a first screening cycle followed by 2D approaches of combinatorial chemistry.     

The Si-B chromophore: A joint experimental and theoretical investigation

Silylboranes with aromatic substituents linked to boron and silicon exhibit an unexpected absorption band in the UV-Vis spectral region. When polar groups were introduced, a marked solvatochromic effect was observed in their fluorescence emission spectra, revealing a strong excited state dipole moment. Semi-empirical MNDO/d and AM1 calculations showed that, upon UV excitation, the polarity of the Si-B bond increased and the aromatic π-electrons migrated toward the Si-B bond, consistent with experimental observations.     

Electronic delocalization in discotic liquid crystals: a joint experimental and theoretical study

Discotic liquid crystals emerge as very attractive materials for organic-based (opto)electronics as they allow efficient charge and energy transport along self-organized molecular columns. Here, angle-resolved photoelectron spectroscopy (ARUPS) is used to investigate the electronic structure and supramolecular organization of the discotic molecule, hexakis(hexylthio)diquinoxalino[2,3-a:2',3'-c]phenazine, deposited on graphite. The ARUPS data reveal significant changes in the electronic properties when going from disordered to columnar phases, the main feature being a decrease in ionization potential by 1.8 eV following the appearance of new electronic states at low binding energy. This evolution is rationalized by quantum-chemical calculations performed on model stacks containing from two to six molecules, which illustrate the formation of a quasi-band structure with Bloch-like orbitals delocalized over several molecules in the column. The ARUPS data also point to an energy dispersion of the upper pi-bands in the columns by some 1.1 eV, therefore highlighting the strongly delocalized nature of the pi-electrons along the discotic stacks.     

FT-IR and NMR investigation of 1-phenylpiperazine: a combined experimental and theoretical study

FT-IR and (1)H, (13)C, DEPT, COSY, NOESY, HETCOR, INADEQUATE NMR spectra of 1-phenylpiperazine (pp) have been reported for the first time except for its (1)H NMR spectrum. The vibrational frequencies and (1)H, (13)C NMR chemical shifts of pp (C(10)H(14)N(2)) have been calculated by means of the Hartree-Fock (HF) and Becke-Lee-Yang-Parr (BLYP) or Becke-3-Lee-Yang-Parr (B3LYP) density functional methods with 6-31G(d) and 6-31G(d,p) basis sets, respectively. Comparison between the experimental and the theoretical results indicates that density functional B3LYP method is superior to the scaled HF and BLYP approach for predicting vibrational frequencies and NMR properties.     

Lanthanide polyoxocationic complexes: experimental and theoretical stability studies and Lewis acid catalysis

The [ε-PMo(V)(8)Mo(VI)(4)O(36)(OH)(4){Ln(III)(H(2)O)}(4)](5+) (Ln=La, Ce, Nd, Sm) polyoxocations, called εLn(4), have been synthesized at room temperature as chloride salts soluble in water, MeOH, EtOH, and DMF. Rare-earth metals can be exchanged, and (31)P NMR spectroscopic studies have allowed a comparison of the affinity of the reduced {ε-PMo(12)} core, thus showing that the La(III) ions have the highest affinity and that rare earths heavier than Eu(III) do not react with the ε-Keggin polyoxometalate. DFT calculations provide a deeper insight into the geometries of the systems studied, thereby giving more accurate information on those compounds that suffer from disorder in crystalline form. It has also been confirmed by the hypothetical La→Gd substitution reaction energy that Ln ions beyond Eu cannot compete with La in coordinating the surface of the ε-Keggin molybdate. Two of these clusters (Ln=La, Ce) have been tested to evidence that such systems are representative of a new efficient Lewis acid catalyst family. This is the first time that the catalytic activity of polyoxocations has been evaluated.     

Unmasking melon by a complementary approach employing electron diffraction, solid-state NMR spectroscopy, and theoretical calculations-structural characterization of a carbon nitride polymer

Poly(aminoimino)heptazine, otherwise known as Liebig's melon, whose composition and structure has been subject to multitudinous speculations, was synthesized from melamine at 630 degrees C under the pressure of ammonia. Electron diffraction, solid-state NMR spectroscopy, and theoretical calculations revealed that the nanocrystalline material exhibits domains well-ordered in two dimensions, thereby allowing the structure solution in projection by electron diffraction. Melon ([C(6)N(7)(NH(2))(NH)](n), plane group p2 gg, a=16.7, b=12.4 A, gamma=90 degrees, Z=4), is composed of layers made up from infinite 1D chains of NH-bridged melem (C(6)N(7)(NH(2))(3)) monomers. The strands adopt a zigzag-type geometry and are tightly linked by hydrogen bonds to give a 2D planar array. The inter-layer distance was determined to be 3.2 A from X-ray powder diffraction. The presence of heptazine building blocks, as well as NH and NH(2) groups was confirmed by (13)C and (15)N solid-state NMR spectroscopy using (15)N-labeled melon. The degree of condensation of the heptazine core was further substantiated by a (15)N direct excitation measurement. Magnetization exchange observed between all (15)N nuclei using a fp-RFDR experiment, together with the CP-MAS data and elemental analysis, suggests that the sample is mainly homogeneous in terms of its basic composition and molecular building blocks. Semiempirical, force field, and DFT/plane wave calculations under periodic boundary conditions corroborate the structure model obtained by electron diffraction. The overall planarity of the layers is confirmed and a good agreement is obtained between the experimental and calculated NMR chemical shift parameters. The polymeric character and thermal stability of melon might render this polymer a pre-stage of g-C(3)N(4) and portend its use as a promising inert material for a variety of applications in materials and surface science.     

Solution and solid-state effects on NMR chemical shifts in sesquiterpene lactones: NMR, X-ray, and theoretical methods

Selected guaianolide type sesquiterpene lactones were studied combining solution and solid-state NMR spectroscopy with theoretical calculations of the chemical shifts in both environments and with the X-ray data. The experimental (1)H and (13)C chemical shifts in solution were successfully reproduced by theoretical calculations (with the GIAO method and DFT B3LYP 6-31++G**) after geometry optimization (DFT B3LYP 6-31 G**) in vacuum. The GIPAW method was used for calculations of solid-state (13)C chemical shifts. The studied cases involved two polymorphs of helenalin, two pseudopolymorphs of 6α-hydroxydihydro-aromaticin and two cases of multiple asymmetric units in crystals: one in which the symmetry-independent molecules were connected by a series of hydrogen bonds (geigerinin) and the other in which the symmetry-independent molecules, deprived of any specific intermolecular interactions, differed in the conformation of the side chain (badkhysin). Geometrically different molecules present in the crystal lattices could be easily distinguished in the solid-state NMR spectra. Moreover, the experimental differences in the (13)C chemical shifts corresponding to nuclei in different polymorphs or in geometrically different molecules were nicely reproduced with the GIPAW calculations.     

Dye aggregation and influence of pre-micelles on heterogeneous catalysis: A photophysical approach

Common cationic dyes used for laser and fluorescent probes present low solubility in water. In order to increase the dye concentration in aqueous solutions, anionic surfactant can be added. The strong interaction between anionic surfactant and cationic dye can affect drastically the dye absorption and fluorescence properties. Here we observed that the fluorescence of the species in aqueous solution is maximized at condition of complete micellization of surfactants at critical micelle concentration (CMC). In addition, combined measurements of absorption, emission and fluorescence lifetime provide fundamental information on the critical concentration of H-aggregates formation and monomer separation, induced by pre-micelles and homomicelles on different surfactant sodium dodecylsulphate (SDS) concentration. The experimental results show how to find precisely the critical concentration of H-aggregates by optical method in two different xanthene-derived molecules: rhodamine 6G and rhodamine B. The adequate transference of electron from excited dye to the conduction band of semiconductor (TiO₂) promotes the creation of reactive species that provides the degradation of dye with advantage of use of irradiation in the visible region and strong photobleaching with direct exposure to the visible light irradiation in a scale of time of 10 min.