Water Formation in Non-Hydrolytic Sol-Gel Routes: Selective Synthesis of Tetragonal and Monoclinic Mesoporous Zirconia as a Case Study.

Several non-hydrolytic sol-gel syntheses involving different precursors, oxygen donors, and conditions have been screened aiming to selectively produce mesoporous t-ZrO2 or m-ZrO2 with significant specific surface areas. The in situ water formation was systematically investigated by Karl Fisher titration of the syneresis liquids. XRD and nitrogen physisorption were employed to characterize the structure and texture of the ZrO2 samples. Significant amounts of water were found in several cases, notably in the reactions of Zr(OnPr)4 with ketones (acetone, 2-pentanone, acetophenone), and of ZrCl4 with alcohols (benzyl alcohol, ethanol) or acetone. Conversely, the reactions of Zr(OnPr)4 with acetic anhydride or benzyl alcohol at moderate temperature (200 °C) and of ZrCl4 with diisopropyl ether appear strictly non-hydrolytic. Although reaction time and reaction temperature were also important parameters, the presence of water played a crucial role on the structure of the final zirconia: t-ZrO2 is favored in strictly non-hydrolytic routes, while m-ZrO2 is favored in the presence of significant amounts of water. 1 H and 13 C NMR analysis of the syneresis liquids allowed us to identify the main reactions responsible for the formation of water and of the oxide network. The morphology of the most interesting ZrO2 samples was further investigated by electron microscopy (SEM, TEM).

Heterogeneous Single-Site Catalysts for C-H Activation Reactions: Pd(II)-Loaded S,O-Functionalized Metal Oxide-Bisphosphonates.

Heterogeneous single-site catalysts contain spatially isolated, well-defined active sites. This allows not only their easy recovery by solid-liquid separation but also the detailed active site design similar to homogeneous catalysts. Here, heterogeneous Pd(II) single-site catalysts were assembled, based on mesoporous metal oxide-bisphosphonate materials as supports. This new family of hybrid organic-inorganic materials with tunable porosity was further functionalized with thioether ligands containing S,O-binding sites that enhance the activity of Pd(II) for C-H activation reactions. The structures of the resulting Pd(II) single-site catalysts were carefully analyzed via solid-state NMR spectroscopy, via texture analysis by N2 physisorption, infrared spectroscopy, and transmission electron microscopy. Furthermore, the immediate environment of the isolated Pd(II) active sites was studied with X-ray absorption spectroscopy. A clear relationship between the thioether ligand surface density and catalyst activity could be established. Significantly higher yields were obtained using highly porous metal oxide-bisphosphonate materials as supports compared to materials with lower porosities, such as conventional metal oxides, indicating that the high surface area facilitates the presence of isolated, well-accessible S,O-supported Pd(II) active sites. A wide scope of model substrates, including industrially relevant arenes, can be converted with high yields by the optimal heterogeneous Pd catalyst.

Dehydration of Alginic Acid Cryogel by TiCl4 vapor: Direct Access to Mesoporous TiO2 @C Nanocomposites and Their Performance in Lithium-Ion Batteries.

A new strategy for the synthesis of mesoporous TiO2 @C nanocomposites through the direct mineralization of seaweed-derived alginic acid cryogel by TiCl4 through a solid/vapor reaction pathway is presented. In this synthesis, alginic acid cryogel can have multiple roles; i) mesoporous template, ii) carbon source, and iii) oxygen source for the TiO2 precursor, TiCl4 . The resulting TiO2 @alginic acid composite was transformed either into pure mesoporous TiO2 by calcination or into mesoporous TiO2 @C nanocomposites by pyrolysis. By comparing with a nonporous TiO2 @C composite, the importance of the mesopores on the performance of electrodes for lithium-ion batteries based on mesoporous TiO2 @C composite was clearly evidenced. In addition, the carbon matrix in the mesoporous TiO2 @C nanocomposite also showed electrochemical activity versus lithium ions, providing twice the capacity of pure mesoporous TiO2 or alginic acid-derived mesoporous carbon (A600). Given the simplicity and environmental friendliness of the process, the mesoporous TiO2 @C nanocomposite could satisfy the main prerequisites of green and sustainable chemistry while showing improved electrochemical performance as a negative electrode for lithium-ion batteries.

One-step nonhydrolytic sol-gel synthesis of mesoporous TiO2 phosphonate hybrid materials.

Mesoporous TiO2-octylphosphonate hybrid materials were prepared in one step by a nonhydrolytic sol-gel method involving the reaction of Ti(OiPr)4, acetophenone (2 equiv) and diethyl octylphosphonate (from 0 to 0.2 equiv) at 200 °C for 12 hours, in toluene. The different samples were characterized by 31P magic angle spinning nuclear magnetic resonance, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and nitrogen physisorption. For P/Ti ratios up to 0.1, the hybrid materials can be described as aggregated, roughly spherical, crystalline anatase nanoparticles grafted by octylphosphonate groups via Ti-O-P bonds. The crystallite size decreases with the P/Ti ratio, leading to an increase of the specific surface area and a decrease of the pore size of the hybrid samples. For a P/Ti ratio of 0.2, the volume fraction of organic octyl groups exceeds 50%. The hybrid material becomes nonporous and can be described as amorphous TiO2 clusters modified by octylphosphonate units, where the octyl chains form an organic continuous matrix.

Acetic Anhydride as an Oxygen Donor in the Non-Hydrolytic Sol-Gel Synthesis of Mesoporous TiO2 with High Electrochemical Lithium Storage Performances.

An original, halide-free non-hydrolytic sol-gel route to mesoporous anatase TiO2 with hierarchical porosity and high specific surface area is reported. This route is based on the reaction at 200 °C of titanium(IV) isopropoxide with acetic anhydride, in the absence of a catalyst or solvent. NMR spectroscopic studies indicate that this method provides an efficient, truly non-hydrolytic and aprotic route to TiO2 . Formation of the oxide involves successive acetoxylation and condensation reactions, both with ester elimination. The resulting TiO2 materials were nanocrystalline, even before calcination. Small (about 10 nm) anatase nanocrystals spontaneously aggregated to form mesoporous micron-sized particles with high specific surface area (240 m2 g-1 before calcination). Evaluation of the lithium storage performances shows a high reversible specific capacity, particularly for the non-calcined sample with the highest specific surface area favouring pseudo-capacitive storage: 253 mAh g-1 at 0.1 C and 218 mAh g-1 at 1 C (C=336 mA g-1 ). This sample also shows good cyclability (92 % retention after 200 cycles at 336 mA g-1 ) with a high coulombic efficiency (99.8 %). Synthesis in the presence of a solvent (toluene or squalane) offers the possibility to tune the morphology and texture of the TiO2 nanomaterials.

Tuning Texture and Morphology of Mesoporous TiO2 by Non-Hydrolytic Sol-Gel Syntheses.

The development of powerful synthetic methodologies is paramount in the design of advanced nanostructured materials. Owing to its remarkable properties and low cost, nanostructured TiO2 is widely investigated for applications such as photocatalysis, energy conversion or energy storage. In this article we report the synthesis of mesoporous TiO2 by three different non-hydrolytic sol-gel routes, and we investigate the influence of the synthetic route and of the presence and nature of the solvent on the structure, texture and morphology of the materials. The first route is the well-known ether route, based on the reaction of TiCl4 with iPr2O. The second and third routes, which have not been previously described for the synthesis of mesoporous TiO2, involve the reaction of Ti(OiPr)4 with stoichiometric amounts of acetophenone and benzoic anhydride, respectively. All materials are characterized by XRD, N2 physisorption and SEM. By playing with the non-hydrolytic route used and the reaction conditions (presence of a solvent, nature of the solvent, calcination), it is possible to tune the morphology and texture of the TiO2. Depending on the reaction conditions, a large variety of mesoporous TiO2 nanostructures could be obtained, resulting from the spontaneous aggregation of TiO2 nanoparticles, either rounded nanoparticles, platelets or nanorods. These nanoparticle networks exhibited a specific surface area up to 250 m² g-1 before calcination, or up to 110 m² g-1 after calcination.

Ethers as Oxygen Donor and Carbon Source in Non-hydrolytic Sol-Gel: One-Pot, Atom-Economic Synthesis of Mesoporous TiO2 -Carbon Nanocomposites.

Mesoporous TiO2 -carbon nanocomposites were synthesized using an original non-hydrolytic sol-gel (NHSG) route, based on the reaction of simple ethers (diisopropyl ether or tetrahydrofuran) with titanium tetrachloride. In this atom-economic, solvent-free process, the ether acts not only as an oxygen donor but also as the sole carbon source. Increasing the reaction temperature to 180 °C leads to the decomposition of the alkyl chloride by-product and to the formation of hydrocarbon polymers, which are converted to carbon by pyrolysis under argon. The carbon-TiO2 nanocomposites and their TiO2 counterparts (obtained by calcination) were characterized by nitrogen physisorption, XRD, solid state 13 C NMR and Raman spectroscopies, SEM, and TEM. The nanocomposites are mesoporous with surface areas of up to 75 m2 g-1 and pore sizes around 10 nm. They are composed of aggregated anatase nanocrystals coated by an amorphous carbon film. Playing on the nature of the ether and on the reaction temperature allows control over the carbon content in the nanocomposites. The nature of the ether also influences the size of the TiO2 crystallites and the morphology of the nanocomposite. To further characterize the carbon coating, the behavior of the carbon-TiO2 nanocomposites and bare TiO2 samples toward lithium insertion-deinsertion was investigated in half-cells. This simple NHSG approach should provide a general method for the synthesis of a wide range of carbon-metal oxide nanocomposites.

Alginic acid aquagel as a template and carbon source in the synthesis of Li4Ti5O12/C nanocomposites for application as anodes in Li-ion batteries.

We report here a simple process for the synthesis of Li4Ti5O12(LTO)/carbon nanocomposites by a one-pot method using an alginic acid aquagel as a template and carbon source, and lithium acetate and TiO2 nanoparticles as precursors to the LTO phase. The carbon content can be tuned by adjusting the relative amount of alginic acid. The obtained materials consist of nanosized primary particles of LTO (30 nm) forming micron-sized aggregates covered by well-dispersed carbon (from 3 to 19 wt%). The homogeneous dispersion of carbon over the particles improves the electrochemical performance of LTO electrodes such as rate capability (>95 mA h g-1 at 40C) and cycling performance (>98% of retention after 500 cycles at 5C), even with only 3% of carbon black additive in the electrode formulation. With a simple and easily up-scalable synthesis, the LTO/carbon nanocomposites of this study are promising candidates as anode materials for practical application in lithium-ion batteries.

Phase transfer of TiO2 nanoparticles from water to ionic liquid triggered by phosphonic acid grafting.

Controlling the interface between TiO2 nanocrystals and ionic liquids is of high fundamental and applied interest for energy storage and conversion devices. Phase transfer of nanoparticles from a synthesis medium to a processing or an application medium plays a significant role in nanotechnology. Here we demonstrate that surface modification with phosphonic acids bearing cationic end-groups can trigger the phase transfer of TiO2 nanoparticles from an aqueous sol to a typical water-immiscible ionic liquid, [Emim][NTf2]. The transfer involves both the grafting of the phosphonic acid moiety and the exchange of the counter ion of the cationic end-group by NTf2 anions, as demonstrated by solid-state NMR, elemental analysis and independent grafting and ion exchange experiments. Furthermore, the colloidal stability of the TiO2 sols in [Emim][NTf2] strongly depends on the hydrophobic character of the cationic end-groups.

Adsorption of benzoxaboroles on hydroxyapatite phases.

UNLABELLED: Benzoxaboroles are a family of molecules that are finding an increasing number of applications in the biomedical field, particularly as a "privileged scaffold" for the design of new drugs. Here, for the first time, we determine the interaction of these molecules with hydroxyapatites, in view of establishing (i) how benzoxaborole drugs may adsorb onto biological apatites, as this could impact on their bioavailability, and (ii) how apatite-based materials can be used for their formulation. Studies on the adsorption of the benzoxaborole motif (C7H7BO2, referred to as BBzx) on two different apatite phases were thus performed, using a ceramic hydroxyapatite (HAceram) and a nanocrystalline hydroxyapatite (HAnano), the latter having a structure and composition more similar to the one found in bone mineral. In both cases, the grafting kinetics and mechanism were studied, and demonstration of the surface attachment of the benzoxaborole under the form of a tetrahedral benzoxaborolate anion was established using (11)B solid state NMR (including (11)B-(31)P correlation experiments). Irrespective of the apatite used, the grafting density of the benzoxaborolates was found to be low, and more generally, these anions demonstrated a poor affinity for apatite surfaces, notably in comparison with other anions commonly found in biological media, such as carboxylates and (organo)phosphates. The study was then extended to the adsorption of a molecule with antimicrobial and antifungal properties (3-piperazine-bis(benzoxaborole)), showing, on a more general perspective, how hydroxyapatites can be used for the development of novel formulations of benzoxaborole drugs. STATEMENT OF SIGNIFICANCE: Benzoxaboroles are an emerging family of molecules which have attracted much attention in the biomedical field, notably for the design of new drugs. However, the way in which these molecules, once introduced in the body, may interact with bone mineral is still unknown, and the possibility of associating benzoxaboroles to calcium phosphates for drug-formulation purposes has not been looked into. Here, we describe the first study of the adsorption of benzoxaboroles on hydroxyapatite, which is the main mineral phase present in bone. We describe the mode of grafting of benzoxaboroles on this material, and show that they only weakly bind to its surface, especially in comparison to other ionic species commonly found in physiological media, such as phosphates and carboxylates. This demonstrates that administered benzoxaborole drugs are unlikely to remain adsorbed on hydroxyapatite surfaces for long periods of time, which means that their biodistribution will not be affected by such phenomena. Moreover, this work shows that the formulation of benzoxaborole drugs by association to calcium phosphates like hydroxyapatite will lead to a rapid release of the molecules.

Formulation of benzoxaborole drugs in PLLA: from materials preparation to in vitro release kinetics and cellular assays.

Benzoxaboroles are a family of organoboron molecules, which have been finding over the past few years an increasing number of biological applications, notably for the design of new drugs. Given that these molecules are still relatively new in the biomedical context, very few investigations regarding their formulation have been reported to date. Here, a complete study on the formulation of benzoxaboroles in a biopolymer, poly-l-lactic acid (PLLA), is reported. The incorporation of two small benzoxaboroles, namely the simplest benzoxaborole molecule (BBzx) and the antifungal drug tavaborole (AN2690), inside PLLA films was investigated. Different variations in the film composition and texture were looked into, by performing a heat-treatment on the PLLA films, or by preparing PLLA-PEO (polyethylene oxide) blends or PLLA-LDH (layered double hydroxide) composites. In each case, the impact of these changes in formulation on the local environment of the benzoxaboroles in the material (as determined by multinuclear solid state NMR), and on the kinetics of release in physiological media were analyzed, showing that a variety of release profiles could be achieved. Finally, cellular assays were carried out looking at the migration of MDA-MB-231 cancer cells. These tests revealed for the first time that benzoxaboroles like AN2690 and BBzx inhibited the migration of these cells. Moreover, the molecules incorporated in the films were found to remain active, and their effect on cancer cells was directly related to the release kinetics from the films. All in all, PLLA-based materials appear as highly versatile and attractive matrices for formulating benzoxaborole-based drugs.

Simultaneous Phase Transfer and Surface Modification of TiO2 Nanoparticles Using Alkylphosphonic Acids: Optimization and Structure of the Organosols.

An original protocol of simultaneous surface modification and transfer from aqueous to organic phases of anatase TiO2 nanoparticles (NPs) using alkylphosphonic acids (PAs) is studied. The influence of the solvent, the nature and concentration of the PA, and the size, concentration, and aggregation state of the TiO2 NPs was investigated. Complete transfer was observed for linear alkyl chains (5, 8, 12, and 18 C atoms), even at very high sol concentrations. After transfer, the grafted NPs were characterized by (31)P solid-state MAS NMR. The dispersion state of NPs before and after phase transfer was monitored by dynamic light scattering (DLS). Small-angle neutron scattering (SANS) was used to characterize the structure of PA-grafted NPs in the organic solvent. Using a quantitative core-shell model cross-checked under different contrast conditions, it is found that the primary particles making up the NPs are homogeneously grafted with a solvated PA-layer. The nanometric thickness of the latter is shown to increase with the length of the linear carbon chain of the PA, independent of the size of the primary TiO2 NP. Interestingly, a reversible temperature-dependent aggregation was evidenced visually for C18PA, and confirmed by DLS and SANS: heating the sample induces the breakup of aggregates, which reassemble upon cooling. Finally, in the case of NPs agglomerated by playing with the pH or the salt concentration of the sols, the phase transfer with PA is capable of redispersing the agglomerates. This new and highly versatile method of NP surface modification with PAs and simultaneous transfer is thus well suited for obtaining well-dispersed grafted NPs.

Surface modification of alumina-coated silica nanoparticles in aqueous sols with phosphonic acids and impact on nanoparticle interactions.

It is often necessary to tailor nanoparticle (NP) interactions and their compatibility with a polymer matrix by grafting organic groups, but the commonly used silanization route offers little versatility, particularly in water. Herein, alumina-coated silica NPs in aqueous sols have been modified for the first time with low molecular-weight phosphonic acids (PAs) bearing organic groups of various hydrophobicities and charges: propyl, pentyl and octyl PAs, and two PAs bearing hydrophilic groups, either a neutral diethylene glycol (DEPA) or a potentially charged carboxylic acid (CAPA) group. The interactions and aggregation in the sols have been investigated using zeta potential measurements, dynamic light scattering, transmission electron microscopy, and small-angle scattering methods. The surface modification has been studied using FTIR and (31)P MAS NMR spectroscopies. Both high grafting density ρ and high hydrophobicity of the groups on the PAs induced aggregation, whereas suspensions of NPs grafted by DEPA remained stable up to the highest ρ. Unexpectedly, CAPA-modified NPs showed aggregation even at low ρ, suggesting that the carboxylic end group was also grafted to the surface. Surface modification of aqueous sols with PAs allows thus for the grafting of a higher density and a wider variety of organic groups than organosilanes, offering an increased control of the interactions between NPs, which is of interest for designing waterborne nanocomposites.

In vitro and in vivo characterization of antibacterial activity and biocompatibility: a study on silver-containing phosphonate monolayers on titanium.

Infections associated with implanted medical devices are a major cause of nosocomial infections, with serious medical and economic repercussions. A variety of silver-containing coatings have been proposed to decrease the risk of infection by hindering bacterial adhesion and biofilm formation. However, the therapeutic range of silver is relatively narrow and it is important to minimize the amount of silver in the coatings, in order to keep sufficient antibacterial activity without inducing cytotoxicity. In this study, the antibacterial efficiency and biocompatibility of nanocoatings with minimal silver loading (∼0.65 nmol cm(-2)) was evaluated in vitro and in vivo. Titanium substrates were coated by grafting mercaptododecylphosphonic acid (MDPA) monolayers followed by post-reaction with AgNO3. The MDPA/AgNO3 nanocoatings significantly inhibited Escherichia coli and Staphylococcus epidermidis adhesion and biofilm formation in vitro, while allowing attachment and proliferation of MC3T3-E1 preosteoblasts. Moreover, osteogenic differentiation of MC3T3 cells and murine mesenchymal stem cells was not affected by the nanocoatings. Sterilization by ethylene oxide did not alter the antibacterial activity and biocompatibility of the nanocoatings. After subcutaneous implantation of the materials in mice, we demonstrated that MDPA/AgNO3 nanocoatings exhibit significant antibacterial activity and excellent biocompatibility, both in vitro and in vivo, after postoperative seeding with S. epidermidis. These results confirm the interest of coating strategies involving subnanomolar amounts of silver exposed at the extreme surface for preventing bacterial adhesion and biofilm formation on metallic or ceramic medical devices without compromising their biocompatibility.

Surface functionalization of detonation nanodiamonds by phosphonic dichloride derivatives.

A new method for the functionalization of detonation nanodiamonds (DNDs) is proposed, on the basis of surface modification with phosphonic dichloride derivatives. DNDs were first modified by phenylphosphonic dichloride, and the grafting modes and hydrolytic stability under neutral conditions were investigated using (1)H, (13)C, and (31)P solid state NMR spectroscopy, Fourier transform infrared spectroscopy, as well as elemental analysis. Then, in order to illustrate the possibilities offered by this method, DNDs functionalized by mesityl imidazolium groups were obtained by postmodification of DNDs modified by 12-bromododecylphosphonic dichloride. The oxidative thermal stability of the functionalized DNDs was investigated using thermogravimetric analysis.

Single- and double-layered organically modified nanosheets by selective interlayer grafting and exfoliation of layered potassium hexaniobate.

Organically modified niobate nanosheets are promising building blocks for the design of advanced hybrid materials. Nanosheets with controlled thickness and surface composition are important for precise structural design of the nanosheet-based materials. In this work, single-layered and double-layered niobate nanosheets functionalized by phenylphosphonate moieties were selectively prepared by interlayer grafting of A-type and B-type intercalation derivatives of potassium hexaniobate (K4Nb6O17·3H2O) with phenylphosphonic acid (PPA), followed by exfoliation by ultrasonication in acetonitrile. The interlayer grafting of PPA was monitored using X-ray diffraction (XRD), Fourier transform infrared (FTIR), and solid-state NMR spectroscopy, and the thicknesses of the exfoliated nanosheets were measured by atomic force microscopy (AFM). Transparent hybrid films were obtained by incorporating the single- and double-layered nanosheets into an epoxy matrix.

Phosphonate coupling molecules for the control of surface/interface properties and the synthesis of nanomaterials.

Phosphonic acids are increasingly being used for controlling surface and interface properties in hybrid or composite materials, (opto)electronic devices and in the synthesis of nanomaterials. In this perspective article, a concise survey of phosphonate coupling molecules is first presented, including details on their coordination chemistry, their use in the surface modification of inorganic substrates with self-assembled monolayers, and the analytical techniques available to characterize their environment in nanomaterials. Then, some of their recent applications in the development of organic electronic devices, photovoltaic cells, biomaterials, biosensors, supported catalysts and sorbents, corrosion inhibitors, and nanostructured composite materials, are presented. In the last part of the article, a brief overview of recent progress in the use of phosphonate ligands for the preparation of molecular nanomaterials like metal organic frameworks and functionalized polyoxometalates is given.

Boronate ligands in materials: determining their local environment by using a combination of IR/solid-state NMR spectroscopies and DFT calculations.

Boronic acids (R-B(OH)(2)) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R-B(OH)(3)(-)) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C(4)H(9)-B(OH)(3)](2), which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid-state NMR spectroscopy ((1)H, (13)C, (11)B and (43)Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave--GIPAW--method). These data allow relationships between the geometry around the OH groups in boronates and the IR and (1)H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic-inorganic materials containing boronate building blocks.

Bonding-induced thermal conductance enhancement at inorganic heterointerfaces using nanomolecular monolayers.

Manipulating interfacial thermal transport is important for many technologies including nanoelectronics, solid-state lighting, energy generation and nanocomposites. Here, we demonstrate the use of a strongly bonding organic nanomolecular monolayer (NML) at model metal/dielectric interfaces to obtain up to a fourfold increase in the interfacial thermal conductance, to values as high as 430 MW m(-2) K(-1) in the copper-silica system. We also show that the approach of using an NML can be implemented to tune the interfacial thermal conductance in other materials systems. Molecular dynamics simulations indicate that the remarkable enhancement we observe is due to strong NML-dielectric and NML-metal bonds that facilitate efficient heat transfer through the NML. Our results underscore the importance of interfacial bond strength as a means to describe and control interfacial thermal transport in a variety of materials systems.

Non-hydrolytic sol-gel routes to heterogeneous catalysts.

Oxides and mixed oxides have a tremendous importance in the field of heterogeneous catalysis, serving either as catalysts or as supports for active species. The performance of a catalyst depends directly on its composition, texture, structure and surface properties, which have to be precisely controlled and adapted to each application. In this context, the sol-gel process is a unique tool for the preparation and understanding of catalytic materials, owing to its exceptional versatility. In the last 10 years, the non-hydrolytic sol-gel (NHSG) or non-aqueous sol-gel process based on nonhydrolytic condensations in nonaqueous media has established itself as a simple and powerful method for the design of a wide range of oxide, mixed oxide and hybrid materials with controlled composition, morphology, texture and structure. NHSG proved particularly interesting for the preparation of catalytic materials, notably mesoporous xerogels, single site catalysts and highly crystalline nanoparticles. This critical review addresses the application of NHSG to the preparation of heterogeneous catalysts, emphasizing the specificities of this process, and giving a comprehensive overview of the literature (251 references).