Unravelling an amine-regulated crystallization crossover to prove single/multicore effects on the biomedical and environmental catalytic activity of magnetic iron oxide colloids.

Elucidation of reaction mechanisms in forming nanostructures is relevant to obtain robust and affordable protocols that can lead to materials with enhanced properties and good reproducibility. Here, the formation of magnetic iron oxide monocrystalline nanoflowers in polyol solvents using N-methyldiethanolamine (NMDEA) as co-solvent has been shown to occur through a non-classical crystallization pathway. This pathway involves intermediate mesocrystals that, in addition, can be transformed into large single colloidal nanocrystals. Interestingly, the crossover of a non-classical crystallization pathway to a classical crystallization pathway can be induced by merely changing the NMDEA concentration. The key is the stability of a green rust-like intermediate complex that modulates the nucleation rate and growth of magnetite nanocrystals. The crossover separates two crystallization domains (classical and non-classical) and three basic configurations (mesocrystals, large and small colloidal nanocrystals). The above finding facilitated the synthesis of magnetic materials with different configurations to suit various engineering applications. Consequently, the effect of the single and multicore configurations of magnetic iron oxide on the biomedical (magnetic hyperthermia and enzyme immobilization) and catalytic activity (Fenton-like reactions and photo-Fenton-like processes driven by visible light irradiation) has been experimentally demonstrated.

Engineering Iron Oxide Nanocatalysts by a Microwave-Assisted Polyol Method for the Magnetically Induced Degradation of Organic Pollutants.

Advanced oxidation processes constitute a promising alternative for the treatment of wastewater containing organic pollutants. Still, the lack of cost-effective processes has hampered the widespread use of these methodologies. Iron oxide magnetic nanoparticles stand as a great alternative since they can be engineered by different reproducible and scalable methods. The present study consists of the synthesis of single-core and multicore magnetic iron oxide nanoparticles by the microwave-assisted polyol method and their use as self-heating catalysts for the degradation of an anionic (acid orange 8) and a cationic dye (methylene blue). Decolorization of these dyes was successfully improved by subjecting the catalyst to an alternating magnetic field (AMF, 16 kA/m, 200 kHz). The sudden temperature increase at the surface of the catalyst led to an intensification of 10% in the decolorization yields using 1 g/L of catalyst, 0.3 M H2O2 and 500 ppm of dye. Full decolorization was achieved at 90 °C, but iron leaching (40 ppm) was detected at this temperature leading to a homogeneous Fenton process. Multicore nanoparticles showed higher degradation rates and 100% efficiencies in four reusability cycles under the AMF. The improvement of this process with AMF is a step forward into more sustainable remediation techniques.

TiO2 Nanostructures as Anode Materials for Li/Na-Ion Batteries.

Here we summarize some results on the use of TiO2 nanostructures as anode materials for more efficient Li-ion (LIBs) and Na-ion (NIBs) batteries. LIBs are the leader to power portable electronic devices, and represent in the short-term the most adequate technology to power electrical vehicles, while NIBs hold promise for large storage of energy generated from renewable sources. Specifically, TiO2 an abundant, low cost, chemically stable and environmentally safe oxide represents in LIBs an alternative to graphite for applications in which safety is mandatory. For NIBs, TiO2 anodes (or more precisely negative electrodes) work at low voltage, assuring acceptable energy density values. Finally, assembling different TiO2 polymorphs in the form of nanostructures decreases diffusion distances, increases the number of contacts and offering additional sites for Na+ storage, helping to improve power efficiency. More specifically, in this contribution we highlighted our work on TiO2 anatase mesocrystals of colloidal size. These sophisticate materials; showing excellent textural properties, have remarkable electrochemical performance as anodes for Li/Na-ion batteries, with conventional alkyl carbonates electrolytes and safe electrolytes based on ionic liquids.

Operando monitoring the nanometric morphological evolution of TiO2 nanoparticles in a Na-ion battery.

Na-ion batteries are nowadays receiving renewed attention because of its propitiousness for large-scale stationary applications. Although the Na storage mechanism is still not completely understood, TiO2 nanoparticles are very promising active anode materials in Na-ion batteries provided that a correct dispersion is achieved within the battery electrode. Whilst the structural changes, either in crystallinity or crystalline phase, that occur during operation are receiving much recent attention, the nanometric morphological evolution of the TiO2 nanoparticles within the electrode is yet to be thoroughly addressed, despite its implication in battery efficiency. In the present work, operando small-angle x-ray scattering studies on TiO2/Na-ion batteries show that whereas the nanoparticle size is preserved during the discharge-charge cycles, the mean distance between nanoparticles increases. The observed morphological changes are consistent with electrode swelling and nanoparticle aggregation during operation, being one phenomenon dominant over the other depending on the applied density current; thus, depending on the differences in ion diffusion within the electrode.

Probing the Catalytic Activity of Sulfate-Derived Pristine and Post-Treated Porous TiO2(101) Anatase Mesocrystals by the Oxidative Desulfurization of Dibenzothiophenes.

Mesocrystals (basically nanostructures showing alignment of nanocrystals well beyond crystal size) are attracting considerable attention for modeling and optimization of functionalities. However, for surface-driven applications (heterogeneous catalysis), only those mesocrystals with excellent textural properties are expected to fulfill their potential. This is especially true for oxidative desulfuration of dibenzothiophenes (hard to desulfurize organosulfur compounds found in fossil fuels). Here, we probe the catalytic activity of anatases for the oxidative desulfuration of dibenzothiophenes under atmospheric pressure and mild temperatures. Specifically, for this study, we have taken advantage of the high stability of the (101) anatase surface to obtain a variety of uniform colloidal mesocrystals (approximately 50 nm) with adequate orientational order and good textural properties (pores around 3-4 nm and surface areas around 200 m2/g). Ultimately, this stability has allowed us to compare the catalytic activity of anatases that expose a high number of aligned single crystal-like surfaces while differing in controllable surface characteristics. Thus, we have established that the type of tetrahedral coordination observed in these anatase mesocrystals is not essential for oxidative desulfuration and that both elimination of sulfates and good textural properties significantly improve the catalytic activity. Furthermore, the most active mesocrystals have been used to model the catalytic reaction in three-(oil-solvent-catalyst) and two-phase (solvent-catalyst) systems. Thus, we have been able to observe that the transfer of DBT from the oil to the solvent phase partially limits the oxidative process and to estimate an apparent activation energy for the oxidative desulfuration reaction of approximately 40 kJ/mol in the two-phase system to avoid mass transfer limitations. Our results clearly establish that (101) anatase mesocrystals with excellent textural properties show adequate stability to withstand several post-treatments without losing their initial mesocrystalline character and therefore could serve as models for catalytic processes different from the one studied here.

Toward a Better Understanding and Optimization of the Electrochemical Activity of Na-Ion TiO2 Anatase Anodes Using Uniform Nanostructures and Ionic Liquid Electrolytes.

TiO2 anatase has emerged as a promising anode for Na-ion batteries (SIBs). However, widespread use of this anode is severely limited by a series of factors that need to be identified and understood to further improve their electrochemical response. Here, we have taken benefit from the versatility of a self-assembly seeding-assisted method to obtain a variety of uniform high-surface-area undoped TiO2 anatase nanostructures. Electrodes built from these uniform nanostructures in combination with a safe ionic liquid electrolyte have allowed a systematic study on some of the factors that determine the electrochemical activity of Na-ion anatase anodes. Interestingly, the inherent low penetrability of the ionic liquid electrolyte has resulted in an unexpected asset to clarify large differences in Na+ uptake by different nanostructures. Basically, solid electrolyte interface (SEI) effects were maximized and therefore clearly separated from electrochemical reactions strictly associated with the anatase anode. Thus, for electrodes built from nanostructures that preserved their initial conformation after cycling, the first discharge showed Na+ uptakes well-beyond those of the Ti4+/Ti3+ redox couple. This large uptake has been associated with an apparent reversible reaction that operates below ca. 0.5-0.7 V and an irreversible mechanism that operates at lower voltages (ca. 0.3 V). However, for electrodes built from nanostructures that favored SEI formation, the irreversible reaction associated with the plateau at ca. 0.3 V was not observed during the first discharge. In accordance, the total Na+ uptake did not reach values beyond those of the corresponding Ti4+/Ti3+ redox couple. Irreversibility, in this case, is associated with SEI formation. Our results also establish the strong effect that size at different scale levels has in the electrochemical response of anatase anodes for SIBs (changes from ca. 6 to 11 nm in crystal sizes and from 50 to 80 in nanostructure sizes led to pronounced differences). This result emphasizes that any conclusions on mechanistic studies other than size effects must be done under strict control on size at various scales (size as a strict control variable at crystal level and nanostructure or in more general terms aggregate scale levels). Finally, we have found that at 30 and 60 °C the performance of the best of the electrodes, with the low-flammable and low-volatile ionic liquid electrolyte, is comparable to that of similar nanostructures immersed in their Li-ion electrolyte counterparts. This result is promising, as in stationary applications where SIBs could replace Li-ion batteries, large accumulation of storage components imposes more strict safety criteria. Basically, power criteria can be relaxed in response to more strict safety criteria.

Dissimilar Crystal Dependence of Vanadium Oxide Cathodes in Organic Carbonate and Safe Ionic Liquid Electrolytes.

Advances in Li metal anode stabilization, solid-state electrolytes, and capabilities to insert a variety of active ions (Li(+), Na(+), Mg(2+), and Al(3+)) have renewed the interest in layered vanadium oxides. Here we show that crystal characteristics such as size and crystallinity are fundamental variables that control the dissimilar electrochemical capabilities of 1D vanadium oxides immersed in different electrolytes (organic carbonates and safe electrolytes containing 80% of ionic liquid). We show that this opposite behavior can be understood in terms of a subtle interplay between crystal characteristics (size and crystallinity), electrolyte degradability, and the ionic conductivity of the electrolyte. Thus, through this control we are able to obtain pure 1D vanadium oxides that show reversibility in carbonate electrolytes at a cutoff voltage of 1.5 V (voltage region where insertion of more than two lithium ions is possible). Furthermore, these materials are able to uptake ca. 1.0 mol of Li at a rate of 20C (1C = 295 mAh/g) and retain excellent capabilities (Coulombic efficiency of 98% after 200 cycles at a rate of 5C). Finally, what, to our knowledge, is really remarkable is that this optimization allows building vanadium oxide electrodes with an excellent electrochemical response in a safe electrolyte composition (80% of ionic liquid). Specifically, we reach uptakes also at a cutoff voltage of 1.5 V of ca. 1.0 mol of Li after 200 cycles at 5C (charge/discharge) with Coulombic efficiencies higher than 99.5%.

Surfactant-Free Vanadium Oxides from Reverse Micelles and Organic Oxidants: Solution Processable Nanoribbons with Potential Applicability as Battery Insertion Electrodes Assembled in Different Configurations.

Vanadium oxides similar to other metal transition oxides are prototypes of multifunctionality. Implementing new synthesis routes that lead to dry vanadium oxide nanomaterials with good functional and structural properties as well as good processing capabilities is thus of general interest. Here we report a facile method based on reverse micelles for the growth at room temperature and atmospheric pressure of surfactant-free vanadium oxide nanoribbons that retain after drying excellent solution-processable capabilities. Essential for the success of the method is the use of a soluble organic oxidant that acts as oxidant and cosurfactant during the synthesis, and facilitates surfactant removal with a simple washing protocol. Interestingly, this simple surfactant removal protocol could be of general applicability. As a proof-of-concept of the functional, structural, and processing capabilities of the dry vanadium oxide nanoribbons here prepared, we have checked their lithium insertion capabilities as battery cathodes built upon different configurations. Specifically, we show efficient insertion both in dry nanoribbons processed as films using doctor blade and organic solvents and in dry nanoribbons infiltrated in three-dimensional metal collectors from aqueous suspensions.

Porous inorganic nanostructures with colloidal dimensions: synthesis and applications in electrochemical energy devices.

Porous inorganic nanostructures with colloidal dimensions can be considered as ideal components of electrochemical devices that operate on renewable energy sources. They combine nanoscale properties with good accessibility, a high number of active sites, short diffusion distances and good processability. Herein, we review some of the liquid-phase routes that lead to the controlled synthesis of these nanostructures in the form of non-hollow, hollow or yolk-shell configurations. From solar and fuel cells to batteries and supercapacitors, we put special emphasis on showing how these sophisticated structures can enhance the efficiency of electrochemical energy devices.

Sub-100 nm TiO2 mesocrystalline assemblies with mesopores: preparation, characterization, enzyme immobilization and photocatalytic properties.

The in situ formation of sub-100 nm solid frameworks stabilized against dissolution by the addition of nanoseeds allows the facile and controllable synthesis of TiO(2) (anatase) mesocrystalline structures with spherical shape, mesoporosity and sizes between 50 and 70 nm. As an example of their multifunctionality, these structures show good capabilities for enzyme immobilization and adequate photocatalytic properties.

Iron oxide nanosized clusters embedded in porous nanorods: a new colloidal design to enhance capabilities of MRI contrast agents.

Development of nanosized materials to enhance the image contrast between the normal and diseased tissue and/or to indicate the status of organ functions or blood flow is essential in nuclear magnetic resonance imaging (MRI). Here we describe a contrast agent based on a new iron oxide design (superparamagnetic iron oxide clusters embedded in antiferromagnetic iron oxide porous nanorods). We show as a proof-of-concept that aqueous colloidal suspensions containing these particles show enhanced-proton relaxivities (i.e., enhanced MRI contrast capabilities). A remarkable feature of this new design is that large scale production is possible since aqueous-based routes are used, and porosity and iron oxide superparamagnetic clusters are directly developed from a single phase. We have also proved with the help of a simple model that the physical basis behind the increase in relaxivities lies on both the increase of dipolar field (interactions within iron oxide clusters) and the decrease of proton-cluster distance (porosity favors the close contact between protons and clusters). Finally, a list of possible steps to follow to enhance capabilities of this contrast agent is also included (partial coating with noble metals to add extra sensing capacity and chemical functionality, to increase the amount of doping while simultaneously carrying out cytotoxicity studies, or to find conditions to further decrease the size of the nanorods and to enhance their stability).

Thermally driven self-assembly of nanomicelles: a facile route to functional monodisperse mesoporous colloidal nanocomposites of inorganic nature and mesoscale size.

Thermally driven self-assembly of nanomicelles can be a feasible route to produce monodisperse porous colloidal nanocomposites of inorganic nature and sizes around the mesoscale (below 100 nm). Success relies on extending the lifetime of intermediate droplets (size below about 100 nm) that are obtained under particular conditions. Herein, the conditions for the long-term stabilization of these unique templates are studied and a model proposed to produce monodisperse porous colloidal nanocomposites. As an example of the potential applications of this methodology, functional colloidal nanocomposites with a high loading of the doping material (30 mol%) are obtained. In particular, superparamagnetic nanomagnets of metallic nature encapsulated in porous oxide colloidal matrixes of mesoscale size that easily respond to an external magnetic field are prepared and characterized in terms of structure and textural and magnetic properties.

Fabrication of mesoporous SiO(2)-C-Fe(3)O(4)/gamma-Fe(2)O(3) and SiO(2)-C-Fe magnetic composites.

A synthetic method for the fabrication of silica-based mesoporous magnetic (Fe or iron oxide spinel) nanocomposites with enhanced adsorption and magnetic capabilities is presented. The successful in situ synthesis of magnetic nanoparticles is a consequence of the incorporation of a small amount of carbon into the pores of the silica, this step being essential for the generation of relatively large iron oxide magnetic nanocrystals ( approximately 10+/-3nm) and for the formation of iron nanoparticles. These composites combine good magnetic properties (superparamagnetic behaviour in the case of SiO(2)-C-Fe(3)O(4)/gamma-Fe(2)O(3) samples) with a large and accessible porosity made up of wide mesopores (>9nm). In the present work, we have demonstrated the usefulness of this kind of composite for the adsorption of a globular protein (hemoglobin). The results obtained show that a significant amount of hemoglobin can be immobilized within the pores of these materials (up to 180mgg(-1) for some of the samples). Moreover, we have proved that the composite loaded with hemoglobin can be easily manipulated by means of an external magnetic field.

Facile and predictable synthesis of dual mesoporous-mesosize nanostructures through thermally-driven self-assembly of nanodroplets.

Dual mesoporous-mesosize nanostructures, of interest in water purification and clean energy generation, are prepared by a facile and predictable method that combines the thermally-driven self-assembly of liquid nanodroplets with gas reactants.

Controlled formation of porous magnetic nanorods via a liquid/liquid solvothermal method.

Porous magnetic nanorods with sizes readily modulated and high water affinity are prepared via a water-in-oil/water solvothermal method.

Signatures of clustering in superparamagnetic colloidal nanocomposites of an inorganic and hybrid nature.

The individual and co-operative properties of inorganic and hybrid superparamagnetic colloidal nanocomposites that satisfy all the requirements of magnetic carriers in the biosciences and/or catalysis fields are been studied. Essential to the success of this study is the selection of suitable synthetic routes (aerosol and nanocasting) that allow the preparation of materials with different matrix characteristics (carbon, silica, and polymers with controlled porosity). These materials present magnetic properties that depend on the average particle size and the degree of polydispersity. Finally, the analysis of the co-operative behavior of samples allows for the detection of signatures of clustering, which are closely related to the textural characteristics of samples and the methodology used to produce the magnetic carriers.

Direct aerosol synthesis of carboxy-functionalized iron oxide colloids displaying reversible magnetic behavior.

A simple and rapid synthetic strategy for fabricating carboxy-functionalized iron oxide colloidal particles displaying reversible magnetic behavior is reported. The method is based on the pyrolysis of aerosols generated from ethanol/water solutions containing iron inorganic salts and mono- or polysaccharides. Essential to the success of the method are the use of hybrid (organo-inorganic) aerosols and the temperature of pyrolysis. The resulting material could be used in advanced biotechnological applications such as the magnetically assisted chemical separation of biocompounds.