Sensor technology has an important effect on many aspects in our society, and has gained much progress, propelled by the development of nanoscience and nanotechnology. Current research efforts are directed toward developing high-performance gas sensors with low operating temperature at low fabrication costs. A gas sensor working at room temperature is very appealing as it provides very low power consumption and does not require a heater for high-temperature operation, and hence simplifies the fabrication of sensor devices and reduces the operating cost. Nanostructured materials are at the core of the development of any room-temperature sensing platform. The most important advances with regard to fundamental research, sensing mechanisms, and application of nanostructured materials for room-temperature conductometric sensor devices are reviewed here. Particular emphasis is given to the relation between the nanostructure and sensor properties in an attempt to address structure-property correlations. Finally, some future research perspectives and new challenges that the field of room-temperature sensors will have to address are also discussed.
This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.
Atomic layer deposition (ALD) is a thin film technology that in the past two decades rapidly developed from a niche technology to an established method. It proved to be a key technology for the surface modification and the fabrication of complex nanostructured materials. In this Progress Report, after a short introduction to ALD and its chemistry, the versatility of the technique for the fabrication of novel functional materials will be discussed. Selected examples, focused on its use for the engineering of nanostructures targeting applications in energy conversion and storage, and on environmental issues, will be discussed. Finally, the challenges that ALD is now facing in terms of materials fabrication and processing will be also tackled.
Surfactant-free nonaqueous (and/or nonhydrolytic) sol-gel routes constitute one of the most versatile and powerful synthesis methodologies for nanocrystalline metal oxides with high compositional homogeneity and purity. Although the synthesis protocols are particularly simple, involving only metal oxide precursors and common organic solvents, the obtained uniform nanocrystals exhibit an immense variety of sizes and shapes. The small number of reactants in these routes enables the study of the chemical mechanisms involved in metal oxide formation. Nonhydrolytic routes to inorganic nanomaterials that used surfactants as size- and shape-controlling agents have been discussed recently. This Minireview supplements this topic by discussing surfactant-free processes, which have become a valuable alternative to surfactant-assisted as well as to traditional aqueous sol-gel chemistry routes.
Galvanic replacement reactions provide a simple and versatile route for producing hollow nanostructures with controllable pore structures and compositions. However, these reactions have previously been limited to the chemical transformation of metallic nanostructures. We demonstrated galvanic replacement reactions in metal oxide nanocrystals as well. When manganese oxide (Mn3O4) nanocrystals were reacted with iron(II) perchlorate, hollow box-shaped nanocrystals of Mn3O4/γ-Fe2O3 ("nanoboxes") were produced. These nanoboxes ultimately transformed into hollow cagelike nanocrystals of γ-Fe2O3 ("nanocages"). Because of their nonequilibrium compositions and hollow structures, these nanoboxes and nanocages exhibited good performance as anode materials for lithium ion batteries. The generality of this approach was demonstrated with other metal pairs, including Co3O4/SnO2 and Mn3O4/SnO2.
Two-dimensional (2D) nanostructures are highly attractive for fabricating nanodevices due to their high surface-to-volume ratio and good compatibility with device design. In recent years 2D nanostructures of various materials including metal oxides, graphene, metal dichalcogenides, phosphorene, BN and MXenes, have demonstrated significant potential for gas sensors. This review aims to provide the most recent advancements in utilization of various 2D nanomaterials for gas sensing. The common methods for the preparation of 2D nanostructures are briefly summarized first. The focus is then placed on the sensing performances provided by devices integrating 2D nanostructures. Strategies for optimizing the sensing features are also discussed. By combining both the experimental results and the theoretical studies available, structure-properties correlations are discussed. The conclusion gives some perspectives on the open challenges and future prospects for engineering advanced 2D nanostructures for high-performance gas sensors devices.
We reveal that the aragonite CaCO3 platelets in nacre of Haliotis laevigata are covered with a continuous layer of disordered amorphous CaCO3 and that there is no protein interaction with this layer. This finding contradicts classical paradigms of biomineralization, e.g., an epitaxial match between the structural organic matrix and the formed mineral. This finding also highlights the role of physicochemical effects in morphogenesis, complementing the previously assumed total control by biomolecules and bioprocesses, with many implications in nanotechnology and materials science.amorphous calcium carbonate ͉ biomineralization ͉ high-resolution transmission EM ͉ solid-state NMR T he delicate mineral structures produced by organisms in the process of biomineralization are widely recognized as inspiration for future materials science and nanotechnology because of their unique materials properties and their hierarchical order often over several length scales (1). Therefore, recent multidisciplinary research has focused on understanding biomineralization processes and exploring ways to mimic them (1). Particularly well investigated is nacre, possessing a 3,000-fold enhanced fracture resistance compared with pure aragonite, with implications on building material design. Nacre is composed of aragonite platelets, a usually metastable CaCO 3 polymorph, with [001] orientation toward protein-covered -chitin layers (2).The present paradigm discusses an epitaxial match of acidic proteins adsorbed on the insoluble matrix with the atomic structure of the aragonite (001) plane (3). Indeed, two independent studies reported aragonite formation in the presence of soluble proteins extracted from a nacreous aragonite biomineral layer (4, 5). However, because the extracted macromolecules are disordered species and mixtures, too (5), an epitaxial match seems questionable. We therefore revisited nacre aragonite single crystalline platelets from the abalone Haliotis laevigata (6) with high-resolution transmission electron microscopy (HRTEM) supplemented by solid-state 13 C and 1 H NMR to obtain information on the organic-inorganic interface. Materials and MethodsNacre was obtained from the shell of the abalone H. laevigata, which belongs to the gastropoda. The structure of the nacreous layer is described in refs. 6-8. Thin cuts from the nacreous part were made with a diamond knife in a Leica ultracut UCT and transferred onto an amorphous carbon-coated copper grid. By using this technique, artifacts in the form of amorphous regions in the sample as can be observed by the ion milling technique (9) can be avoided. A Philips CM200 FEG transmission electron microscope, operating at 200 kV, equipped with a field emission gun was used. Alternatively, a JEOL 4010 operated at 400 kV equipped with a LaB 6 cathode was applied. The NMR experiments have been carried out by using an AVANCE 600 spectrometer (Bruker, Billerica, MA) using a double-resonant 7-mm probe at sample rotation magic angle spinning (MAS) frequencies of 6.5 kHz.1 H MAS NMR spectr...
Innovative strategies to produce well-defined nanoparticles and other nanostructures such as nanofibres, quantum wells and mesoporous materials have revitalized materials science for the potential benefit to society. Here, we report a controlled process, involving soft-chemistry-based deposition, template-assisted mesostructured growth, and tuned annealing conditions that allows the preparation of ordered mesoporous crystalline networks and mesostructured nano-island single layers, composed of multicationic metal oxides having perovskite, tetragonal or ilmenite structures. This strategy to obtain meso-organized multi-metal-oxide nanocrystalline films (M(3)NF) bridges the gap between conventional mesoporous materials and the remarkable properties of crystalline ternary or quaternary metallic oxides. Nanocrystalline mesoporous films with controlled wall thickness (10-20 nm) of dielectric SrTiO(3), photoactive MgTa(2)O(6) or ferromagnetic semi-conducting Co(x)Ti(1-x)O(2-x) were prepared by evaporation-induced self-assembly (EISA) using a specially designed non-ionic block-copolymer template. A tuned thermal treatment of the mesoporous films permits the transfer of the wall structure into nanocrystallites, with all tectonic units being tightly incorporated into mechanically stable ordered tri- or bidimensional nanocrystalline networks. This methodology should allow multifunctionalization, miniaturization and integration during development of devices such as smart sensors and actuators, better-performing photocatalysts, and fast electrochromic devices. On the other hand, organized arrays of dispersed ferromagnetic or ferroelectric nanoparticles are promising materials for spintronics and for cheap, non-volatile 'flash' memories.
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