Microalgae as Soft Permeable Particles.

The colloidal stability of non-motile algal cells in water drives their distribution in space. An accurate description of the interfacial properties of microalgae is therefore critical to understand how microalgae concentrations can change in their biotope or during harvesting processes. Here, we probe the surface charges of three unicellular algae─Chlorella vulgaris, Nannochloropsis oculata, and Tetraselmis suecica─through their electrophoretic mobility. Ohshima's soft particle theory describes the electrokinetic properties of particles covered by a permeable polyelectrolyte layer, a usual case for biological particles. The results appear to fit the predictions of Ohshima's theory, proving that all three microalgae behave electrokinetically as soft particles. This allowed us to estimate two characteristic parameters of the polyelectrolyte external layer of microalgae: the volume charge density and the hydrodynamic penetration length. Results were compared with transmission electron microscopy observations of the algal cells' surfaces, and in particular of their extracellular polymeric layer, which was identified with the permeable shell evidenced by electrophoretic measurements. Noticeably, the algal surface potentials estimated from electrophoretic mobility using the soft particle theory are less negative than the apparent zeta potentials. This finding indicates that electrostatics are expected to play a minor role in phenomena of environmental and industrial importance, such as microalgae aggregation or adhesion.

Magnetic structure and internal field nuclear magnetic resonance of cobalt nanowires.

The magnetic properties of cobalt metal nanowires grown by electrodeposition in porous membranes depend largely on the synthesis conditions. Here, we focus on the role of electrolyte additives on the magnetic anisotropy of the electrodeposited nanowires. Through magnetometry and internal field nuclear magnetic resonance (IF NMR) studies, we compared both the magnetic and crystalline structures of 50 and 200 nm diameter Co nanowires synthesized in the presence or absence of organic additives. The spectral characteristics of IF NMR were compared structurally to X-ray diffraction patterns, and the anisotropy of the NMR enhancement factor in ferromagnetic multidomain structures to magnetometry results. While the magnetic behavior of the 50 nm nanowires was dominated, as expected, by shape anisotropy with magnetic domains oriented on axis, the analysis of the 200 nm proved to be more complex. 59Co IF NMR revealed that the determining difference between the samples electrodeposited in the presence or in absence of organic additives was not the dominant crystalline system (fcc or hcp) but the coherent domain sizes and boundaries. In the presence of organic additives, the cobalt crystal domains are smaller and with defective grain boundaries, as revealed by resonances below 210 MHz. This prevented the development in the Co hcp part of the sample of the strong magnetocrystalline anisotropy that was observed in the absence of organic additives. In the presence of organic additives, even in nanowires as wide as 200 nm, the magnetic behavior remained determined by the shape anisotropy with a positive effective magnetic anisotropy and strong anisotropy of the NMR enhancement factor.

Extreme Enhancement of Carbon Hydrogasification via Mechanochemistry.

Carbon hydrogasification is the slowest reaction among all carbon-involved small-molecule transformations. Here, we demonstrate a mechanochemical method that results in both a faster reaction rate and a new synthesis route. The reaction rate was dramatically enhanced by up to 4 orders of magnitude compared to the traditional thermal method. Simultaneously, the reaction exhibited very high selectivity (99.8 % CH4 , versus 80 % under thermal conditions) with a cobalt catalyst. Our study demonstrated that this extreme increase in reaction rate originates from the continuous activation of reactive carbon species via mechanochemistry. The high selectivity is intimately related to the activation at low temperature, at which higher hydrocarbons are difficult to form. This work is expected to advance studies of carbon hydrogasification, and other solid-gas reactions.

Superparamagnetic behaviour of metallic Co nanoparticles according to variable temperature magnetic resonance.

Investigating the size distributions of Co nanoparticle ensembles is an important problem, which has no straightforward solution. In this work, we use the combination of 59Co internal field nuclear magnetic resonance (59Co IF NMR) and ferromagnetic resonance (FMR) spectroscopies on a metallic Co nanoparticle sample with a narrow Co nanoparticle size distribution due to encapsulation within the inner channels of carbon nanotubes. High-resolution transmission electron microscopy (TEM) images showed that the nanoparticles can be represented as prolate spheroids, with the majority of particles having an aspect ratio between 1 and 2. This observation has increased the accuracy of superparamagnetic blocking size calculations from Néel relaxation model by introducing the actual volume of the ellipsoids taken from the image processing. 59Co IF NMR and FMR experiments conducted under different temperatures allowed us to observe the thermal blocking of superparamagnetic particles in full accordance with the TEM particle volume distribution. This proved that these magnetic resonance techniques can be used jointly for characterization of Co nanoparticles in the bulk of the sample.

Hydrophobization of Silica Nanoparticles in Water: Nanostructure and Response to Drying Stress.

We report on the impact of surface hydrophobization on the structure of aqueous silica dispersions and how this structure resists drying stress. Hydrophilic silica particles were hydrophobized directly in water using a range of organosilane precursors, with a precise control of the grafting density. The resulting nanostructure was precisely analyzed by a combination of small-angle X-ray scattering (SAXS) and cryo-microscopy (cryo-TEM). Then, the dispersion was progressively concentrated by drying, and the evolution of the nanostructures as a function of the grafting density was followed by SAXS. At the fundamental level, because the hydrophobic character of the silica surfaces could be varied continuously through a precise control of the grafting density, we were able to observe how the hydrophobic interactions change particles interactions and aggregates structures. Practically, this opened a new route to tailor the final structure, the residual porosity, and the damp-proof properties of the fully dried silica. For example, regardless of the nature of the hydrophobic precursor, a grafting density of 1 grafter per nm2 optimized the interparticle interactions in solution in view to maximize the residual porosity in the dried material (0.9 cm3/g) and reduced the water uptake to less than 4% in weight compared to the typical value of 13% for hydrophilic particles (at T = 25 °C and relative humidity = 80%).

Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of (29)Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

Thermal stability and hcp-fcc allotropic transformation in supported Co metal catalysts probed near operando by ferromagnetic NMR.

Despite the fact that cobalt based catalysts are used at the industrial scale for Fischer-Tropsch synthesis, it is not yet clear which cobalt metallic phase is actually at work under operando conditions and what is its state of dispersion. As it turns out, the different phases of metallic cobalt, fcc and hcp, give rise to distinct ferromagnetic nuclear magnetic resonance. Furthermore, within one Co metal particle, the occurrence of several ferromagnetic domains of limited sizes can be evidenced by the specific resonance of Co in multi-domain particles. Consequently, by ferromagnetic NMR, one can follow quantitatively the sintering and phase transitions of dispersed Co metal particles in supported catalysts under near operando conditions. The minimal size probed by ferromagnetic Co NMR is not precisely known but is considered to be in the order of 10 nm for supported Co particles at room temperature and increases to about 35 nm at 850 K. Here, in Co metal Fischer-Tropsch synthesis catalysts supported on ß-SiC, the resonances of the fcc multi-domain, fcc single-domain and hcp Co were clearly distinguished. A careful rationalization of their frequency and width dependence on temperature allowed a quantitative analysis of the spectra in the temperature range of interest, thus reflecting the state of the catalysts under near operando conditions that is without the uncertainty associated with prior quenching. The allotropic transition temperature was found to start at 600-650 K, which is about 50 K below the bulk transition temperature. The phase transition was fully reversible and a significant part of the hcp phase was found to be stable up to 850 K. This anomalous behavior that was observed without quenching might prove to be crucial to understand and model active species not only in catalysts but also in battery materials.

Flow properties of MK-based geopolymer pastes. A comparative study with standard Portland cement pastes.

Geopolymers are presented in many studies as alternatives to ordinary Portland cement. Previous studies have focused on their chemical and mechanical properties, their microstructures and their potential applications, but very few have focussed on their rheological behaviour. Our work highlights the fundamental differences in the flow properties, which exist between geopolymers made from metakaolin and Ordinary Portland Cement (OPC). We show that colloidal interactions between metakaolin particles are negligible and that hydrodynamic effects control the rheological behaviour. Metakaolin-based geopolymers can then be described as Newtonian fluids with the viscosity controlled mainly by the high viscosity of the suspending alkaline silicate solution and not by the contribution of direct contacts between metakaolin grains. This fundamental difference between geopolymers and OPC implies that developments made in cement technology to improve rheological behaviour such as plasticizers will not be efficient for geopolymers and that new research directions need to be explored.

Micrometer scale resolution of materials by stray-field Magnetic Resonance Imaging.

As Magnetic Resonance Imaging devices are becoming more and more powerful, resolutions as small as 10 µm can now be obtained. But, this is only possible when systems with slow transverse relaxation rates, like living tissues, are investigated. In this case, the time available for gradients space-encoding is long, and high k values can be reached in the Fourier domain. However, numerous materials have fast relaxation rates, thus limiting the spatial resolution to a few hundreds of microns. The Stray Field Imaging technique has solved this problem by using a very high (typically 5000 G/cm) static gradient. Consequently, the trajectory in k space is accelerated and it is possible, in principle, to reach a micrometer resolution in a few hundreds of microseconds. Most of the time, however, only resolutions in the millimeter range can be achieved due to mispositioning of the sample within the static magnetic field. Here, we show that by finely mapping the magnetic field and precisely positioning the sample, it is possible with a standard spectrometer to reach a micrometer resolution even on very fast relaxing materials.

Chemical and physicochemical investigation of an aminoalkylalkoxysilane as strengthening agent for cellulosic materials.

AMDES (aminopropylmethyldiethoxysilane) was used to investigate the physicochemical and chemical events related to the introduction of aminoalkylalkoxysilanes in cellulosic materials. Using (29)Si CP-MAS and (1)H NMR to study the reactivity and structural modification of AMDES in the paper it was shown that polymerization occurs in situ. The distribution of the active compound on the surface of the fibers and throughout the fibers' thickness was visualized by SEM-EDS. A relation between moisture content, fiber swelling, and uptake of AMDES was found. To better represent old and brittle documents, the paper was predegraded by oxidation with sodium hypochlorite. XRD confirmed the advanced destruction of the amorphous areas of cellulose. Adding AMDES in the oxidized paper resulted in improved mechanical properties, a roughly unmodified degree of polymerization of cellulose, but a slight increase in the yellowing, probably due to several possible reaction products such as imines, amine, amides, and Maillard reactions products. The deacidification efficacy was established and the strengthening effect was shown to arise from the interaction of AMDES with the cellulose fibers.

Density functional theory calculations of 95Mo NMR parameters in solid-state compounds.

The application of periodic density functional theory-based methods to the calculation of (95)Mo electric field gradient (EFG) and chemical shift (CS) tensors in solid-state molybdenum compounds is presented. Calculations of EFG tensors are performed using the projector augmented-wave (PAW) method. Comparison of the results with those obtained using the augmented plane wave + local orbitals (APW+lo) method and with available experimental values shows the reliability of the approach for (95)Mo EFG tensor calculation. CS tensors are calculated using the recently developed gauge-including projector augmented-wave (GIPAW) method. This work is the first application of the GIPAW method to a 4d transition-metal nucleus. The effects of ultra-soft pseudo-potential parameters, exchange-correlation functionals and structural parameters are precisely examined. Comparison with experimental results allows the validation of this computational formalism.

MAS NMR spectra of quadrupolar nuclei in disordered solids: the Czjzek model.

Structural disorder at the scale of two to three atomic positions around the probe nucleus results in variations of the EFG and thus in a distribution of the quadrupolar interaction. This distribution is at the origin of the lineshape tailing toward high fields which is often observed in the MAS NMR spectra of quadrupolar nuclei in disordered solids. The Czjzek model provides an analytical expression for the joint distribution of the NMR quadrupolar parameters upsilon(Q) and eta from which a lineshape can be predicted. This model is derived from the Central Limit Theorem and the statistical isotropy inherent to disorder. It is thus applicable to a wide range of materials as we have illustrated for 27Al spectra on selected examples of glasses (slag), spinels (alumina), and hydrates (cement aluminum hydrates). In particular, when relevant, the use of the Czjzek model allows a quantitative decomposition of the spectra and an accurate extraction of the second moment of the quadrupolar product. In this respect, it is important to realize that only rotational invariants such as the quadrupolar product can make sense to describe the quadrupolar interaction in disordered solids.

129Xe nuclear magnetic resonance study of pitch-based activated carbon modified by air oxidation/pyrolysis cycles: a new approach to probe the micropore size.

(129)Xe NMR has been used to study a series of homologous activated carbons obtained from a KOH-activated pitch-based carbon molecular sieve modified by air oxidation/pyrolysis cycles. A clear correlation between the pore size of microporous carbons and the (129)Xe NMR of adsorbed xenon is proposed for the first time. The virial coefficient delta(Xe)(-)(Xe) arising from binary xenon collisions varied linearly with the micropore size and appeared to be a better probe of the microporosity than the chemical shift extrapolated to zero pressure. This correlation was explained by the fact that the xenon collision frequency increases with increasing micropore size. The chemical shift has been shown to vary very little with temperature (less than 9 ppm) for xenon trapped inside narrow and wide micropores. This is indicative of a smooth xenon-surface interaction potential.

"Cooking the sample": radiofrequency induced heating during solid-state NMR experiments.

Dissipation of radiofrequency (RF) energy as heat during continuous wave decoupling in solid-state NMR experiment was examined outside the conventional realm of such phenomena. A significant temperature increase could occur while performing dynamic NMR measurements provided the sample contains polar molecules and the sequence calls for relatively long applications of RF power. It was shown that the methyl flip motion in dimethylsulfone (DMS) is activated by the decoupling RF energy conversion to heat during a CODEX pulse sequence. This introduced a significant bias in the correlation time-temperature dependency measurement used to obtain the activation energy of the motion. By investigating the dependency of the temperature increase in hydrated lead nitrate on experimental parameters during high-power decoupling one-pulse experiments, the mechanisms for the RF energy deposition was identified. The samples were heated due to dissipation of the energy absorbed by dielectric losses, a phenomenon commonly known as "microwave" heating. It was thus established that during solid-state NMR experiments at moderate B0 fields, RF heating could lead to the heating of samples containing polar molecules such as hydrated polymers and inorganic solids. In particular, this could result in systematic errors for slow dynamics measurements by solid-state NMR.

95Mo magic angle spinning NMR at high field: improved measurements and structural analysis of the quadrupole interaction in monomolybdates and isopolymolybdates.

In this study, 95Mo quadrupole couplings in various molydbates were measured easily and accurately with magic angle spinning (MAS) NMR under a directing field of 19.6 T. The resonance frequency of 54 MHz was sufficiently high to remove acoustic ringing artifacts, and the spectra could be analyzed in the usual terms of chemical shift and quadrupolar line shapes. For monomolybdates and molybdite, the quadrupole coupling dominated the NMR response, and the quadrupole parameters could be measured with better accuracy than in previous lower field studies. Moreover, despite the low symmetry of the molybdenum coordination, the usefulness of such measurements to probe molybdenum environments was established by ab initio density functional theory (DFT) calculations of the electric field gradient from known structures. The experimental NMR data correlated perfectly with the refined structures. In isopolymolybdates, the resonances were shapeless and DFT calculations were impossible because of the large and low symmetry unit cells. Nevertheless, empirical but clear NMR signatures were obtained from the spinning sidebands analysis or the MQMAS spectra. This was possible for the first time thanks to the improved baseline and sensitivity at high fields. With the generalization of NMR spectrometers operating above 17 T, it was predicted that 95Mo MAS NMR could evolve as a routine characterization tool for ill-defined structures such as supported molybdates in catalysis.