Cédric Gommes

Sulfonated silica/carbon nanocomposites as novel catalysts for hydrolysis of cellulose to glucose

Sulfonated silica/carbon nanocomposites were successfully developed as reusable, solid acid catalysts for the hydrolytic degradation of cellulose into high yields of glucose.

Quantitative structural analysis of binary nanocrystal superlattices by electron tomography

Binary nanocrystal superlattices, that is, ordered structures of two sorts of nanocolloids, hold promise for a series of functional materials with novel collective properties. Here we show that based on electron tomography a comprehensive, quantitative, three-dimensional characterization of these systems down to the single nanocrystal level can be achieved, which is key in understanding the emerging materials properties. On four binary lattices composed of PbSe, CdSe, and Au nanocrystals, we illustrate that ambiguous interpretations based on two-dimensional transmission electron microscopy can be prevented, nanocrystal sizes and superlattice parameters accurately determined, individual crystallographic point and plane defects studied, and the order/disorder at the top and bottom surfaces imaged. Furthermore, our results suggest that superlattice nucleation and growth occurred at the suspension/air interface and that the unit cells of some lattices are anisotropically deformed upon drying.

ConeX: a program for angular calibration and averaging of two-dimensional powder scattering patterns

CONEX is a Windows application for converting series of two-dimensional X-ray powder patterns measured on flat two-dimensional detectors into one-dimensional scattering patterns. It is based on the rigorous use of scattering patterns of calibration samples to determine the three-dimensional position of the detector, with respect to the sample and to the beam. This enables correction of the data for geometric distortions, even when the detector is highly tilted and not centred on the beam.

Nanoparticle Growth in Supported Nickel Catalysts during Methanation Reaction—Larger is Better†

A major cause of supported metal catalyst deactivation is particle growth by Ostwald ripening. Nickel catalysts, used in the methanation reaction, may suffer greatly from this through the formation of [Ni(CO)4 ]. By analyzing catalysts with various particle sizes and spatial distributions, the interparticle distance was found to have little effect on the stability, because formation and decomposition of nickel carbonyl rather than diffusion was rate limiting. Small particles (3-4 nm) were found to grow very large (20-200 nm), involving local destruction of the support, which was detrimental to the catalyst stability. However, medium sized particles (8 nm) remained confined by the pores of the support displaying enhanced stability, and an activity 3 times higher than initially small particles after 150 h. Physical modeling suggests that the higher [Ni(CO)4 ] supersaturation in catalysts with smaller particles enabled them to overcome the mechanical resistance of the support. Understanding the interplay of particle size and support properties related to the stability of nanoparticles offers the prospect of novel strategies to develop more stable nanostructured materials, also for applications beyond catalysis.

Image analysis characterization of multi-walled carbon nanotubes

An original image analysis method is presented to characterize multi-walled carbon nanotubes from transmission electron microscopy images. The analysis is performed in three steps: (i) image preprocessing in order to isolate the nanotubes from the background, (ii) image segmentation, aiming at keeping only the measurable sections of nanotubes, and finally (iii) tube characteristics measurement. The measurement is based on a Lambert-like electron absorption law and is performed on the original gray level image itself. Two geometrical and one physical characteristics are determined for each tube, namely, its outer and inner radius and a linear electron absorption coefficient. The method is illustrated by comparing a pristine and an annealed carbon nanotube samples. The compaction of the tube walls during annealing is shown to result from a lowering of the external radius while the inner radius is left unchanged.

Adsorption, capillary bridge formation, and cavitation in SBA-15 corrugated mesopores: a Derjaguin-Broekhoff-de Boer analysis.

A Derjaguin-Broekhoff-de Boer analysis of adsorption and desorption in SBA-15 mesoporous silica is presented, using realistic geometrical models that account for the pore corrugation in these materials. The model parameters are derived from independent electron tomography and small-angle scattering characterization. A geometrical characteristic of the pore that is found to be important for adsorption is the corrugation length, l(C), which describes the longitudinal size of the geometrical defects along a given pore. Capillary bridges are possible only for large values of l(C). The results are explained in terms of two spinodal and two equilibrium pressures, characterizing the wide and the narrow sections of the pores. Simplified analytical expressions are obtained, which provide necessary conditions for bridge formation and for cavitation in terms of the radii of the narrow and wide sections of the pores, as well as of l(C). Quite generally, the results show that the deviation of the pore shape from that of ideal cylinders is key to understanding adsorption and desorption in corrugated mesopores, notably in SBA-15.

Molecular and Morphological Aspects of Annealing-Induced Stabilization of Starch Crystallites

A unique series of potato (mutant) starches with highly different amylopectin/amylose (AP/AM) ratios was annealed in excess water at stepwise increasing temperatures to increase the starch melting (or gelatinization) temperatures in aqueous suspensions. Small-angle X-ray scattering (SAXS) experiments revealed that the lamellar starch crystals gain stability upon annealing via thickening for high-AM starch, whereas the crystal surface energy decreases for AM-free starch. In starches with intermediate AP/AM ratio, both mechanisms occur, but the surface energy reduction mechanism prevails. Crystal thickening seems to be associated with the cocrystallization of AM with AP, leading to very disordered nanomorphologies for which a new SAXS data interpretation scheme needed to be developed. Annealing affects neither the crystal internal structure nor the spherulitic morphology on a micrometer length scale.

Revealing the Formation of Copper Nanoparticles from a Homogeneous Solid Precursor by Electron Microscopy

The understanding of processes leading to the formation of nanometer-sized particles is important for tailoring of their size, shape and location. The growth mechanisms and kinetics of nanoparticles from solid precursors are, however, often poorly described. Here we employ transmission electron microscopy (TEM) to examine the formation of copper nanoparticles on a silica support during the reduction by H2 of homogeneous copper phyllosilicate platelets, as a prototype precursor for a coprecipitated catalyst. Specifically, time-lapsed TEM image series acquired of the material during the reduction process provide a direct visualization of the growth dynamics of an ensemble of individual nanoparticles and enable a quantitative evaluation of the nucleation and growth of the nanoparticles. This quantitative information is compared with kinetic models and found to be best described by a nucleation-and-growth scenario involving autocatalytic reduction of the copper phyllosilicate followed by diffusion-limited or reaction-limited growth of the copper nanoparticles. The plate-like structure of the precursor restricted the diffusion of copper and the autocatalytic reduction limited the probability for secondary nucleation. The combination of a uniform size of precursor particles and the autocatalytic reduction thus offers means to synthesize nanoparticles with well-defined sizes in large amounts. In this way, in situ observations made by electron microscopy provide mechanistic and kinetic insights into the formation of supported nanoparticles, essential for the rational design of nanomaterials.

Density of States for a Specified Correlation Function and the Energy Landscape

The degeneracy of two-phase disordered microstructures consistent with a specified correlation function is analyzed by mapping it to a ground-state degeneracy. We determine for the first time the associated density of states via a Monte Carlo algorithm. Our results are explained in terms of the roughness of an energy landscape, defined on a hypercubic configuration space. The use of a Hamming distance in this space enables us to define a roughness metric, which is calculated from the correlation function alone and related quantitatively to the structural degeneracy. This relation is validated for a wide variety of disordered structures.

Increased aortic compliance maintains left ventricular performance at lower energetic cost.

OBJECTIVE The aim of this study was to investigate left ventricular contractility and energetic cost of cardiac ejection under conditions of acute increase in aortic compliance. METHODS In six anaesthetized pigs, ascending aortic compliance was increased by adding a volume chamber in parallel to the ascending aorta. Systemic vascular parameters, including characteristic impedance, peripheral resistance, total vascular compliance, and inertance, were estimated with a four-element windkessel model. Arterial elastance was derived from these parameters. Left ventricular systolic function was assessed by end-systolic pressure-volume relationship (end-systolic elastance), and stroke work. Pressure-volume area was used as a measure of myocardial oxygen consumption. Heart rate remained constant during the experimentation. RESULTS Adding the aortic volume chamber significantly increased vascular compliance from 0. 95+/-0.08 to 1.17+/-0.06 ml/mmHg (P<0.01), while inductance, characteristic impedance, peripheral resistance, and arterial elastance remained statistically at basal values, respectively 0. 0020+/-0.0003 mmHg.s(2)/ml, 0.105+/-0.009 mmHg.s/ml, 1.27+/-0.12 mmHg.s/ml, and 2.43+/-0.21 mmHg/ml. During the same interval, stroke work and pressure-volume area decreased respectively from 2700+/-242 to 2256+/-75 mmHg.ml (P<0.01), and from 3806+/-427 to 3179+/-167 mmHg.ml (P<0.01). Stroke work and pressure-volume area decreased at matched end-diastolic volumes. In contrast, end-systolic elastance, ejection fraction, and stroke volume remained statistically unchanged, respectively at 2.29+/-0.14 mmHg/ml, 48.1+/-2.1 %, and 32. 4+/-1.7 ml. CONCLUSIONS These data suggest that, when facing an increased aortic compliance, the left ventricle displays unchanged contractility, but the energetic cost of cardiac ejection is significantly decreased. These data may be of clinical importance when choosing an artificial prosthesis for ascending aortic replacement.