In Situ Characterization of Mixtures of Linear and Branched Hydrocarbons Confined within Porous Media Using 2D DQF-COSY NMR Spectroscopy.

The analysis of 1D anti-diagonal spectra from the projections of 2D double-quantum filtered correlation spectroscopy NMR spectra is presented for the determination of the compositions of liquid mixtures of linear and branched alkanes confined within porous media. These projected spectra do not include the effects of line broadening and therefore retain high-resolution information even in the presence of inhomogeneous magnetic fields as are commonly found in porous media. A partial least-square regression analysis is used to characterize the mixture compositions. Two case studies are considered. First, mixtures of 2-methyl alkanes and n-alkanes are investigated. It is shown that estimation of the mol % of branched species present was achieved with a root-mean-square error of prediction (RMSEP) of 1.4 mol %. Second, the quantification of multicomponent mixtures consisting of linear alkanes and 2-, 3-, and 4-monomethyl alkanes was considered. Discrimination of 2-methyl and linear alkanes from other branched isomers in the mixture was achieved, although discrimination between 3- and 4- monomethyl alkanes was not possible. Compositions of the linear alkane, 2-methyl alkane, and the total composition of 3- and 4-methyl alkanes were estimated with a RMSEP <3 mol %. The approach was then used to estimate the composition of the mixtures in terms of submolecular groups of CH3CH2, (CH3)2CH, and CH2CH(CH3)CH2 present in the mixtures; a RMSEP <1 mol % was achieved for all groups. The ability to characterize the mixture compositions in terms of molecular subgroups allows the application of the method to characterize mixtures containing multimethyl alkanes. The motivation for this work is to develop a method for determining the mixture composition inside the catalyst pores during Fischer-Tropsch synthesis. However, the method reported is generic and can be applied to any system in which there is a need to characterize mixture compositions of linear and branched alkanes.

In Situ Determination of Carbon Number Distributions of Mixtures of Linear Hydrocarbons Confined within Porous Media Using Pulsed Field Gradient NMR.

Pulsed field gradient (PFG) NMR measurements, combined with a novel optimization method, are used to determine the composition of hydrocarbon mixtures of linear alkanes (C7-C16) in both the bulk liquid state and when imbibed within a porous medium of mean pore diameter 28.6 nm. The method predicts the average carbon number of a given mixture to an accuracy of ±1 carbon number and the mole fraction of a mixture component to within an average root-mean-square error of ±0.036 with just three calibration mixtures. Given that the method can be applied at any conditions of temperature and pressure at which the PFG NMR measurements are made, the method has the potential for application in characterizing hydrocarbon liquid mixtures inside porous media and at the operating conditions relevant to, for example, hydrocarbon recovery and heterogeneous catalysis.

Exploring the origins of turbulence in multiphase flow using compressed sensing MRI.

Ultrafast magnetic resonance imaging, employing spiral reciprocal space sampling and compressed sensing image reconstruction, is used to acquire velocity maps of the liquid phase in gas-liquid multiphase flows. Velocity maps were acquired at a rate of 188 frames per second. The method enables quantitative characterization of the wake dynamics of single bubbles and bubble swarms. To illustrate this, we use the new technique to demonstrate the role of bubble wake vorticity in driving bubble secondary motions, and in governing the structure of turbulence in multiphase flows.

Three-dimensional morphology of iron oxide nanoparticles with reactive concave surfaces. A compressed sensing-electron tomography (CS-ET) approach.

In this paper, we apply electron tomography (ET) to the study of the three-dimensional (3D) morphology of iron oxide nanoparticles (NPs) with reactive concave surfaces. The ability to determine quantitatively the volume and shape of the NP concavity is essential for understanding the key-lock mechanism responsible for the destabilization of gold nanocrystals within the iron oxide NP concavity. We show that quantitative ET is enhanced greatly by the application of compressed sensing (CS) techniques to the tomographic reconstruction. High-fidelity tomograms using a new CS-ET algorithm reveal with clarity the concavities of the particle and enable 3D nanometrology studies to be undertaken with confidence. In addition, the robust performance of the CS-ET algorithm with undersampled data should allow rapid progress with time-resolved 3D nanoscale studies, 3D atomic resolution imaging, and cryo-tomography of nanoscale cellular structures.

Surface diffusion in porous catalysts.

This paper presents the application of pulsed field gradient (PFG) nuclear magnetic resonance (NMR) to observe surface diffusion of 1-octene in porous 1 wt% Pd/theta-Al(2)O(3) catalyst trilobes. We demonstrate for the first time the ability to identify diffusion on the pore surfaces unambiguously at ambient conditions in saturated porous media; this technique is applicable to microporous and mesoporous materials in general. At very short observation times, two distinct diffusion regimes are present. These are associated with the bulk pore and pore surface diffusion of 1-octene; using the model proposed by Kärger for two site exchange we determined the diffusion coefficients of these regimes to be 1.3 x 10(-9) and 1.7 x 10(-11) m(2) s(-1), respectively, and the mean residence time of a molecule on the pore surface to be 150 ms. Treatment of the catalyst trilobes with a silane surface coating is seen to influence the surface such that a surface diffusion coefficient is no longer observed, supporting the interpretation that the molecular dynamics of surface diffusing species are influenced strongly by their interaction with hydroxyl groups on the alumina surface. This technique will enable further study and improved understanding of molecular transport in porous catalysts used in liquid-phase, heterogeneous catalytic processes.

Experimental Determination of H2 and CO Diffusion Coefficients in a Wax Mixture Confined in a Porous Titania Catalyst Support.

The ability to measure and predict molecular diffusion coefficients in multicomponent mixtures is not only of fundamental scientific interest but also of significant relevance in understanding how catalytic processes proceed. In the present work, the direct measurement of the molecular diffusion of H2 and CO gas-phase species diffusing in n-alkane mixtures using pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) methods is reported. The work is of direct relevance to Fischer-Tropsch (FT) catalysis, with the measurements being made of the gas-wax system with the wax in both the bulk liquid state and when confined within a titania catalyst support, at temperatures and pressures typical of low-temperature FT synthesis. Molecular diffusion coefficients of H2 and CO within wax-saturated porous titania in the range (1.00-2.43) × 10-8 and (6.44-8.50) × 10-9 m2 s-1, respectively, were measured in the temperature range of 140-240 and 200-240 °C for H2 and CO, respectively, at a pressure of 40 bar. The wax mixture was typical of a wax produced during FT catalysis and had a molar average carbon number of 36. It is shown that the hydrogen diffusion coefficient within this wax mixture is consistent, to within experimental error, with the hydrogen diffusion coefficient measured in pure single-component n-hexatriacontane (n-C36) wax; this result held with the waxes in the bulk liquid state and when confined within the porous titania. The tortuosity of the porous titania was also measured using PFG NMR and found to be 1.77; this value is independent of temperature. The ability of existing correlations to predict these experimentally determined data was then critically evaluated. Although the Wilke-Chang correlation was found to underestimate the molecular diffusion coefficients of both H2 and CO diffusing in the wax in both the bulk state and when confined within the porous titania, parameterized correlations based on the rough hard sphere model, having accounted for the experimentally determined tortuosity factor, predicted the H2 and CO diffusion within bulk and confined wax to within 3%.

Enabling High Spectral Resolution of Liquid Mixtures in Porous Media by Antidiagonal Projections of Two-Dimensional 1H NMR COSY Spectra.

The noninvasive, in situ chemical identification of liquid mixtures confined in porous materials is experimentally challenging. NMR is chemically resolved and applicable to optically opaque systems but suffers from a significant loss in spectral resolution in the presence of the magnetic field inhomogeneities typical of porous media. In this work, we introduce a method of analysis of conventional two-dimensional (2D) 1H NMR correlation spectroscopy (COSY) spectra based on the extraction of 1D antidiagonal projections, which are free from line-broadening effects and can therefore be used for chemical species identification. Here, we show the application of the technique to the measurement of linear n-alkanes where the cross-to-diagonal peak ratios are shown to follow a power-law curve as a function of the chain length. This calibration enables quantifying mixtures of linear hydrocarbons confined in any porous material independently of temperature or inter-molecular dynamics. Thus, this is a promising tool for quantitative chemical reaction monitoring studies in heterogeneous systems under operando experimental conditions.

Spatially-resolved 1H NMR relaxation-exchange measurements in heterogeneous media.

In the last decades, the 1H NMR T2-T2 relaxation-exchange (REXSY) technique has become an essential tool for the molecular investigation of simple and complex fluids in heterogeneous porous solids and soft matter, where the mixing-time-evolution of cross-correlated T2-T2 peaks enables a quantitative study of diffusive exchange kinetics in multi-component systems. Here, we present a spatially-resolved implementation of the T2-T2 correlation technique, named z-T2-T2, based on one-dimensional spatial mapping along z using a rapid frequency-encode imaging scheme. Compared to other phase-encoding methods, the adopted MRI technique has two distinct advantages: (i) is has the same experimental duration of a standard (bulk) T2-T2 measurement, and (ii) it provides a high spatial resolution. The proposed z-T2-T2 method is first validated against bulk T2-T2 measurements on homogeneous phantom consisting of cyclohexane uniformly imbibed in finely-sized α-Al2O3 particles at a spatial resolution of 0.47 mm; thereafter, its performance is demonstrated, on a layered bed of multi-sized α-Al2O3 particles, for revealing spatially-dependent molecular exchange kinetics properties of intra- and inter-particle cyclohexane as a function of particle size. It is found that localised z-T2-T2 spectra provide well resolved cross peaks whilst such resolution is lost in standard bulk T2-T2 data. Future prospective applications of the method lie, in particular, in the local characterisation of mass transport phenomena in multi-component porous media, such as rock cores and heterogeneous catalysts.

In situ reaction monitoring in heterogeneous catalysts by a benchtop NMR spectrometer.

Understanding the reactivity and mass transport properties of porous heterogenous catalysts is important for the development of new materials. Whereas MRI has previously been used to correlate chemical kinetics and hydrodynamics under operando conditions, this paper demonstrates that a modern benchtop NMR spectrometer is a suitable alternative to obtain diverse reaction information in porous heterogeneous catalyst materials on a smaller scale. Besides information about the chemical conversion within the pores, it can also be used to study changes of surface interaction by T1/T2 NMR relaxometry techniques and changes in mass transport by PFG NMR from a single chemical reaction.

Fast spatially-resolved T2 measurements with constant-gradient CPMG.

Speed of acquisition is paramount for the application of magnetic resonance to flow experiments through porous rocks. One popular method for imaging core floods is the spatially resolved T2 experiment which can separate fluids either by their viscosity contrast or by doping one fluid with a relaxation agent. Existing techniques for spatial-T2 may suffer from long acquisition times and eddy currents due to the pulsing of magnetic field gradients. Here, we propose a constant gradient method for 1d spatially-resolved T2 which embraces the speed of frequency encoding techniques and avoids eddy currents by the absence of any gradient ramps during the radio frequency (r.f.) pulse train. We provide the operating envelope for this kind of experiment, which is restricted due to the slice selectivity of the r.f. pulses in the presence of the magnetic field gradient. Additionally, we show that the effects of self-diffusion and the mixing of T1 and T2 contributions are manageable. As an illustration, we have applied this technique to an enhanced oil recovery experiment. The two fluid phases were tracked without any doping and with a time resolution of 40 s. In this case, the increased time resolution allowed us to observe dynamic flow phenomena such as fluid fingering and the calculation of the velocity of the fluid displacement fronts.