
Dominique MassiotFrench National Centre for Scientific Research | CNRS · Institut de Chimie (INC)
Dominique Massiot
Directeur de Recherche
About
433
Publications
47,412
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
19,875
Citations
Introduction
Publications
Publications (433)
Intensive research on improving the catalytic properties of zeolites is focused on modulating their acidity and the distribution of associated Al sites. Herein, by studying a series of ZSM‐5 zeolites over a broad range of Al content, we demonstrate how the nature of the mineralizing agent (F‐ or OH‐) used in hydrothermal syntheses directly impacts...
Intensive research on improving the catalytic properties of zeolites is focused on modulating their acidity and the distribution of associated Al sites. Herein, by studying a series of ZSM‐5 zeolites over a broad range of Al content, we demonstrate how the nature of the mineralizing agent (F⁻ or OH⁻) used in hydrothermal syntheses directly impacts...
Crystallization of oxide glasses rich in Zn2+, Ga3+, and Ge4+ is of interest for the synthesis of new transparent ceramics. In this context, we report the identification and detailed structural characterization of a new solid solution Ca3Ga2-2xZnxGe4+xO14 (0 ≤ x ≤ 1). These compounds adopt the trigonal langasite structure type, offering three possi...
In this letter to the editor we question the origin of the figures in the paper published by M.A.Diop and collaborators, on line since June 28 th 2021 in Metallurgical and Materials Transactions B https://doi.org/10.1007/s11663-021-02223-5
The study of ionic dynamics in solids is essential to understanding and developing modern energy technologies. Here we study the ionic dynamics of orthorhombic Na2MgSiO4, an interesting case of a polar stuffed-cristobalite-type structure that contains two inequivalent Na sites within the channels of the magnesium silicate tetrahedral framework. Its...
Across the evolutionary history of insects, the shift from nitrogen-rich carnivore/omnivore diets to nitrogen-poor herbivorous diets was made possible through symbiosis with microbes. The herbivorous turtle ants Cephalotes possess a conserved gut microbiome which enriches the nutrient composition by recycling nitrogen-rich metabolic waste to increa...
We report the atomic-scale structure of alumina layers obtained by atomic layer deposition (ALD) of trimethylaluminium onto partially dehydroxylated silica. Such a detailed insight into the atomic structure of the species formed with increasing Al content was gained using a variety of one- and two-dimensional solid-state nuclear magnetic resonance...
We present an algorithm suitable for automatically correcting rolling baseline coming from time-domain truncation induced by the dead time in pulse-acquire one-dimensional MAS NMR spectra. It relies on an iterative estimation of the baseline restricted in the time-domain by the dead time duration combined with a histogram filter allowing adaptive s...
The Core Scientific Dataset (CSD) model with JavaScript Object Notation (JSON) serialization is presented as a lightweight, portable, and versatile standard for intra- and interdisciplinary scientific data exchange. This model supports datasets with a p-component dependent variable, {U0, …, Uq, …, Up−1}, discretely sampled at M unique points in a d...
We report the study of high-temperature melts (1600°C-2300°C) and related glasses in the SrO-Al2O3-SiO2 phase diagram considering three series: (i) depolymerized ([SrO]/[Al2O3] = 3); (ii) fully polymerized ([SrO]/[Al2O3] = 1); and (iii) per-aluminous ([SrO]/[Al2O3] < 1). By considering results from high-temperature ²⁷Al NMR and high temperature neu...
An injectable purely apatitic calcium phosphate cement (CPC) was successfully combined to a water-soluble radiopaque agent (i.e., Xenetix®), to result in an optimized composition that was found to be as satisfactory as poly(methyl methacrylate) (PMMA) formulations used for vertebroplasty, in terms of radiopacity, texture and injectability. For that...
In this work, we show that it is possible to overcome the limitations of solid-state MRI for rigid tissues due to large line broadening and short dephasing times by combining Magic Angle Spinning (MAS) with rotating pulsed field gradients. This allows recording ex vivo³¹P 3D and 2D slice-selected images of rigid tissues and related biomaterials at...
Understanding the links between chemical composition, nano-structure and the dynamic properties of silicate melts and glasses is fundamental to both Earth and Materials Sciences. Central to this is whether the distribution of mobile metallic ions is random or not. In silicate systems, such as window glass, it is well-established that the short-rang...
The description of the structure of aluminosilicate glasses is more than often centered on its cationic constituents and oxygen ions determine their connectivity, directly impacting the physical properties of those disordered materials. A very powerful approach to ascertain this short- to medium-range order is to use 17O NMR but up to now the speci...
The atomic scale structure of aluminum in amorphous alumina films processed by direct liquid injection chemical vapor deposition from aluminum tri-isopropoxide (ATI) and dimethyl isopropoxide (DMAI) is investigated by solid-state (27)Al nuclear magnetic resonance (SSNMR) using a very high magnetic field of 20.0 T. This study is performed as a funct...
The room temperature structure of Ba5AlF13 has been investigated by coupling electron, synchrotron and neutron powder diffraction, solid-state high-resolution NMR (¹⁹F and ²⁷Al) and first principles calculations. An initial structural model has been obtained from electron and synchrotron powder diffraction data, and its main features have been conf...
Identifying and characterizing defects in crystalline solids is a challenging problem, particularly for lithium-ion intercalation materials, which often exhibit multiple stable oxidation and spin states as well as local ordering of lithium and charges. Here, we reveal the existence of characteristic lithium defect environments in the crystalline li...
Boron heteroatom distributions are shown to be significantly different in two closely related layered borosilicates synthesized by subtly different alkylammonium surfactant species. The complicated order and disorder near framework boron sites in both borosilicates were characterized at the molecular level by using a combination of multi-dimensiona...
Different possible options were investigated to combine an apatitic calcium phosphate cement with gallium ions, known as bone resorption inhibitors. Gallium can be either chemisorbed onto calcium-deficient apatite or inserted in the structure of β-tricalcium phosphate, and addition of these gallium-doped components into the cement formulation did n...
Five homogeneous arsenic selenide glasses with target compositions As2Se3, AsSe2, AsSe3, AsSe4.5 and AsSe6 were studied quantitatively by 77Se CPMG-MAS-NMR and TEM-EDX. The whole set of NMR spectra is simultaneously fitted with six distinct environments taking into account the effect of first and second neighbors on the position of the 77Se resonan...
Research in chemistry on the frontier of knowledge
“Mixed research units” are building blocks, flexible but permanent, in rapidly evolving fields of research. Several measures shape the activities of research teams and thus give rise to “poles of research”. They also help consolidate national networks, identify strong points, boost the sharing of t...
We have developed new methods enabling in vivo localization and identification of metabolites through their (1)H NMR signatures, in a drosophila. Metabolic profiles in localized regions were obtained using HR-MAS Slice Localized Spectroscopy and Chemical Shift Imaging at high magnetic fields. These methods enabled measurement of metabolite contents...
L’Unité Mixte de Recherche est la brique élémentaire, souple et pérenne d’un paysage de la recherche en évolution rapide. De nombreux dispositifs viennent structurer l’activité de ces équipes pour faire émerger des pôles de recherche, consolider le maillage des réseaux nationaux, identifier les points forts, mutualiser des équipements de haut nivea...
Les faits, longtemps sujets à discussion, sont désormais là. Le cinquième rapport du GIEC (2013) qualifie d'« extrêmement probable » un lien entre les dérèglements climatiques observés depuis 1950 et les variations de la composition de l'atmosphère terrestre provoqués par l'augmentation forte et récente des activités anthropiques. L'implication dir...
Layered silicates have important applications as host materials, supports for catalysis, and zeolite precursors. However, their local structures are often challenging to establish due to disorder of the sheet assemblies. We present a new protocol that combines long- and short-range structural constraints from diffraction and solid-state NMR techniq...
Transparent polycrystalline ceramics present significant economical and functional advantages over single crystal materials for optical, communication, and laser technologies. To date, transparency in these ceramics is ensured either by an optical isotropy (i.e. cubic symmetry) or a nanometric crystallite size, and the main challenge remains to eli...
Aluminum 5-fold coordination coexisting with 4-and 6-fold coordination structurally characterizes amorphous aluminum oxide. For nearly 30 years now, 27Al MAS NMR has enabled to detect and later on to quantify this feature thanks to advances in high-resolution instrumentation. The Introduction shortly reviews the results of investigations of 5-coord...
The nature of γ-alumina (γ-Al2O3) surface sites leaves many open questions today, and solid-state NMR spectroscopy has been proposed and used as a tool for assessing their structure. Here, we calculated 27Al NMR parameters from first principles in periodic boundary conditions for a large number of Al sites with different coordination, potentially p...
The Zerodur® glass-ceramic chemical durability has been studied by leaching. The nuclear magnetic resonance spectroscopy analysis has allowed highlighting the network changes. A macroscopic evaluation of the surface alteration has been performed by contact angle measurements, this analysis being sensible to the roughness and the hydrophilic charact...
The relationship between the experimental 19F isotropic chemical shift and the 19F isotropic shielding calculated using the gauge including projector augmented-wave (GIPAW) method with PBE functional is investigated in the case of GaF3, InF3, TlF and several AlF3 polymorphs. It is shown that the linear correlation between experimental and DFT-PBE c...
Abstract
Silica-supported chloro alkyl aluminum co-catalysts (DEAC@support) were prepared via Surface Organometallic Chemistry by contacting diethylaluminum chloride (DEAC) and high specific surface silica materials, i.e. SBA-15, MCM-41, and Aerosil SiO2. Such systems efficiently activate NiCl2(PBu3)2 for catalytic ethene dimerization, with turnove...
Phase separation in glasses has been extensively studied due to its occurence in silica-rich glasses; however, some aspects as the first steps of the nucleation of domains with different compositions remain to be clarified as they are difficult to characterize with most analytical techniques. Thereafter, it will be demonstrated that these first ste...
New nanostructured gallogermanate-based glass materials exhibiting high transparency in the visible and infrared regions are fabricated by conventional melt-quenching. These materials can accommodate wide oxide compositions and present nanoscale phase separation, in the form of droplets well separated from the germanate matrix. The size of the nano...
Highly transparent nanostructured gallogermanatebased glass and glass-ceramic materials are reported on page 364 by M. Allix and co-workers. These materials present nanoscale phase separations, whose size can be tailored depending on the nominal composition. The large variety of accessible compositions combined with precise control of the nanostruc...
La10W2O21 is prepared by solid state reaction of a stoichiometric mixture of La2O3 and WO3 (alumina crucible, 1550 °C, 12 h).
Because of their importance in both the geosciences and the glass-making industry, alkali
aluminosilicate melts have been the focal point of many past studies, but despite progress many problems remain unresolved, such as the complex behaviour of the thermodynamic properties of
aluminium-rich alkali silicate melts. This paper presents a study of Na...
This work reports the development of a relevant and general method, based on high-frequency impedance measurements, for the in situ monitoring of the alpha-tricalcium phosphate to calcium-deficient hydroxyapatite transformation that is the driving force of the hardening processes of some calcium phosphate cements (CPCs) used as bone substitutes. Th...
The crystal structure of La10W2O21, which has to be reformulated (La5.667W0.333)LaWO14□2, is best described, on average, by a 2 × 2 × 2 anion-deficient fluorite-related superstructure cubic cell, with space group F4̅ 3m, Z = 4, and a = 11.17932(6) Å, similar to Y7ReO14--δ. The 32 cations are distributed with lanthanum on the 4a-site, tungsten on th...
Chalcogenide and chalco-halide glasses containing gallium have been studied through Ga-71 solid state nuclear magnetic resonance (NMR). An unusual line shape of the Ga-71 NMR spectra has been observed for the first time. This line shape was ascribed to the preferential local symmetry existing around gallium atoms in these glasses which are characte...
Nuclear magnetic resonance (NMR) spectroscopy provides information about the structural and dynamic aspects of clay minerals. High-resolution magic angle spinning (MAS)-NMR investigations give specific information about structural networks, crystallographic sites, and cation distributions. Conventional low-resolution NMR techniques are useful for i...
Soda lime silicate oxide glasses are studied to perform coloration thanks to gold nanoparticles’ crystallization. This precipitation is conducted by chemical reduction of gold ions with stannous or antimony oxides as reducing agents. A control of the rendered coloration between blank to red shades has been obtained using Sb2O3 agent and appropriate...
We show that solid-state NMR can probe the structure of crystalline materials when disorder is present and, hence, this provides a method to extend the periodic-based description obtained by diffraction techniques. Reviewing some of our recently published results, we first address the issue of NMR sensitivity using wollastonite CaSiO3. We then cons...
The only easy way to prepare amorphous alumina is via thin film deposition. For this reason, the disorder in amorphous alumina has not yet been fully investigated. We have used very high-field (20 T) solid state 27Al NMR spectroscopy to analyze the structural modifications of amorphous alumina thin films with deposition temperature (Td). The films...
Unlike the long-range order of ideal crystalline structures, local order is an intrinsic characteristic of real materials and often serves as the key to the tuning of their properties and their final applications. Although researchers can easily assess local ordering using two-dimensional imaging techniques with resolution that approaches the atomi...
Triisobutylaluminum reacts with silica yielding three different Al sites according to high-field aluminum-27 NMR and first principle calculations: a quadruply grafted dimeric surface species and two incorporated Al(O)x species (x = 4 or 5). This result is in stark contrast to the bis-grafted species that forms during Et3Al silica grafting. Thus the...
Nuclear spins as spies to explore the structure of materials This article illustrates how solid state NMR, which is by nature a local spectroscopic technique, is also able to establish dialogs between nuclear spins over distances up to few nanometers. Access to such length scales is possible through one-dimensional and multidimensional experiments...
The red long-lasting luminescence properties of the ZnGa2O4:Cr3+ spinel material are shown to be much improved when germanium or tin is substituted to the nominal composition. The resulting Zn1+xGa2–2x(Ge/Sn)xO4 (0 ≤ x ≤ 0.5) spinel solid solutions synthesized here by a classic solid state method have been structurally characterized by X-ray and ne...
Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with 13C and 11B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NM...
Bioactive glasses are able to form strong bonds to bone. This property, crucial for medical applications, depends on the glass composition and structure. Dissolution of phosphates in melt-quenched silicate glasses raises the question of chemical homogeneity and possible formation of clusters. A detailed structural characterization of the bioactive...
This article reports on the identification, synthesis, and in-situ structure determination of a new crystalline calcium borosilicate compound of composition CaSi(1/3)B(2/3)O(8/3). Synthesis was carried out by complete crystallization on annealing from a corresponding glassy composition in the widely studied CaO-SiO(2)-B(2)O(3) ternary system. The c...
We present a detailed investigation of the molecular structure of montmorillonite, an aluminosilicate clay with important applications in materials sciences, such as for catalysis, drug delivery, or as a waste barrier. Solid-state 29Si, 27Al, 25Mg, and 1H nuclear magnetic resonance (NMR) measurements combined with density functional theory (DFT) ca...
We used magic angle spinning (MAS), multiquantum (MQ)-MAS, and high-temperature (HT) nuclear magnetic resonance (NMR) measurements to investigate the oxide-ion conduction path of oxygen-17 (O-17) in apatite-type lanthanum silicate La9.33(SiO4)6O2. A highly crystalline apatite-type lanthanum silicate was specifically synthesized for the measurements...
We have investigated the Al/Si ordering in the pseudoisolated pairs of tetrahedral sites of the structure of crystalline gehlenite Ca2Al2SiO7 by means of 29Si and 27Al NMR and first-principles quantum mechanical calculations. 29Si NMR spectra of isotopically enriched samples enables the precise determination of the population of the two silicon sit...
Lithium self-diffusion coefficients are measured for the first time using (7)Li Pulsed-Field Gradient Nuclear Magnetic Resonance (PFG-NMR) in a crystalline inorganic powder of α-Li(3)N between 534 K and 774 K. The diffusion of lithium cations is anisotropic, and the activation energy for the diffusion within the Li(2)N layers was found to be 0.150...
Natural-abundance 25Mg solid-state NMR data obtained using very high magnetic fields of 17.6, 20.0, and 30.0 T are reported for a series of magnesium phosphate compounds, some of which are of potential biomedical interest. The 25Mg NMR parameters have been calculated by using the DFT PAW and GIPAW methods, for both the experimental and DFT atomic p...
Nuclear spins as spies to explore the structure of materials This article illustrates how solid state NMR, which is by nature a local spectroscopic technique, is also able to establish dialogs between nuclear spins over distances up to few nanometers. Access to such length scales is possible through one-dimensional and multidimensional experiments...
The long-range ordering of a crystalline material can be accurately determined by analyzing the Bragg intensities and positions. In contrast, direct observation of short-range ordering in crystalline materials, which is increasingly considered of fundamental importance to unravel the structure–property relationships that underpin their technologica...
Dipolar-Heteronuclear Multiple Quantum Correlation (D-HMQC) experiment based on SR4(2)(1) recoupling was shown as a very efficient probe of spatial proximities in ordered or disordered materials. As crystalline sodium silicates have been extensively studied using 1D and 2D MAS NMR experiments and DFT calculations, they have been used as candidate m...
The determination of the nature and structure of surface sites after chemical modification of large surface area oxides such as silica is a key point for many applications and challenging from a spectroscopic point of view. This has been, for instance, a long-standing problem for silica reacted with alkylaluminum compounds, a system typically studi...
The synthesis and structure resolution of RbLaF(4) are described. RbLaF(4) is synthesized by solid-state reaction between RbF and LaF(3) at 425 °C under a nonoxidizing atmosphere. Its crystal structure has been resolved by combining neutron and synchrotron powder diffraction data refinements (Pnma,a = 6.46281(2) Å, b = 3.86498(1) Å, c = 16.17629(4)...