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The worldwide energy scarcity arising from the massive consumption of nonrenewable energy sources raised a global awareness of the need for cleaner and affordable energy solutions to mitigate climate change and ensure the world sustainable development. The rise of the Internet of Things and the fast growth of the groundbreaking market of wearable electronics boosted a major quest for self-powered technologies merging energy harvesting and energy storage functionalities to meet the demands of a myriad of market segments, such as healthcare, transportation, defense and sports. Thermoelectric devices are a green energy harvesting solution for wearable electronics since they harness the low-grade waste heat from ubiquitous thermal energy sources and convert it into electrical energy. However, these systems generate electrical energy in an intermittent manner, depend on the local heat release availability and require an additional unit to store energy. Flexible and wearable supercapacitors are a safe and eco-friendly energy storage solution to power wearables, offering advantages of security, longer cycle life, higher power density and faster charging over batteries. However, an additional unit that generates energy or that is able to charge the storage device is required. More recently, a new class of all-in-one thermally-chargeable supercapacitors blossomed to meet the requirements of the next generation of autonomous wearable electronics and ensure an endurable energy supply. This self-chargeable hybrid technology combines the functionalities of thermal energy harvesting and supercapacitive energy storage in a single multitasking device. In this Perspective, the advances in the burgeoning field of all-in-one thermally-chargeable supercapacitors for flexible/wearable applications will be critically examined, ranging from their structure and working principle to the rational design of the composing materials and of tailor-made architectures. It will start by introducing the foundations of single flexible/wearable thermoelectric generators and supercapacitors and will evolve into the pioneering venture of fully-integrated thermal energy harvesting/storage systems. It will end by highlighting the current bottlenecks and future pathways for advancing the development of this sophisticated smart technology. [ABSTRACT FROM AUTHOR]

Raman spectroscopy is highly sensitive to the morphology and electronic structures of graphitic materials, but a convenient interpretation model has been lacking for multiwalled carbon nanotubes (MWCNTs), in particular for the discrimination of spectral changes induced by covalent functionalization. The present work describes a systematic investigation of the Raman analysis of covalently functionalized MWCNTs by diazonium chemistry and oxidation methodologies, with typically different mechanisms and reaction sites. A multi-peak deconvolution system and spectral band assignment were proposed based on the chemical and structural modifications identified by X-ray photoelectron spectroscopy, thermogravimetry, X-ray diffraction, specific surface areas and the comparative analysis of the first and second order regions of the Raman spectra. Diazonium functionalization takes place mainly in the π-system of the external sidewall, while oxidation occurs on defects and leads to structure burning. This allowed us to distinguish between spectral features related to aromaticity disruptions within the sidewalls and spectral features related to changes within the inner tubes. The model was validated extending the studies to the functionalization of MWCNTs by the Bingel reaction. [ABSTRACT FROM AUTHOR]

This work reports the mastered design of novel water-dispersible superparamagnetic iron oxide nanomaterials with enhanced magnetic properties and reduced size. A straightforward cost-effective aqueous coprecipitation route was developed, based on the use of three new coprecipitation agents: the polydentate bases diethanolamine, triethanolamine and triisopropanolamine. Through the selection of these alkanolamines which presented different complexing properties, an improvement of the surface spin order could be achieved upon the reduction of the nanomaterial dimensions (from 8.7 to 3.8 nm) owing to the complexation of the polydentate bases with the subcoordinated iron cations on the particle surface. In particular, the alkanolamine with the highest chelating ability (triethanolamine) led to the nanomaterial with the smallest size and the thinnest magnetic “dead” layer. In order to evaluate the importance of the dual control of size and magnetism, the relaxometric properties of the nanomaterials were investigated, whereby maximum values of transverse relaxivity r2 of 300.30 and 253.92 mM−1 s−1 at 25 and 37 °C, respectively (at 20 MHz) were achieved, making these nanomaterials potential T2-weighted MRI contrast agents. Moreover, these values were significantly higher than those reported for commercial T2 contrast agents and other iron oxides with identical dimensions. Hence, we were able to demonstrate that the r2 enhancement cannot only be achieved by an increase of particle/cluster size, but also through the precise control of the surface magnetic properties while constraining the nanomaterial dimensions. These achievements open up new perspectives on the mastered design of magnetic nanoprobes, overcoming the limitations related to the deleterious effect of size reduction. [ABSTRACT FROM AUTHOR]

This work reports the tailored design of novel mixed ferrite nanoparticles, CoxMn1−xFe2O4 (x = 0, 0.3, 0.7, and 1), through an optimized one-pot aqueous coprecipitation process. The influence of the substitution between Mn(ii) and Co(ii) and of the alkaline agent, isopropanolamine (MIPA) or NaOH, on the morphological, chemical and magnetic properties of the nanomaterials was investigated. The joint action between chemical substitution and type of alkaline agent allowed a precise tuning of the particle size, magnetic properties and inversion degree of the spinel structure. A wide range of particle dimensions (from 3 to 30 nm) and saturation magnetization (from 57 to 71 emu g−1) was achieved. The increase of Co(ii) content from x = 0 to x = 1 led to a systematic decrease of the particle size, regardless of the base type, which could be modelled by an exponential decay function. For each Co : Mn composition, the use of MIPA instead of the traditional NaOH promoted a three times reduction of the particle size and simultaneously switched the magnetic state of the CoxMn1−xFe2O4 nanomaterials from ferromagnetic to superparamagnetic. These results constitute a step forward in the challenging quest for high-performance magnetic nanoprobes by an eco-friendly synthesis route. [ABSTRACT FROM AUTHOR]

NiO nanoparticles (NPs) were prepared by a sol–gel process using the citrate route. The sol–gel parameters were tuned to obtain samples with different average particle sizes, ranging from 12 to 70 nm. Magnetic characterization revealed an increase in the blocking temperature with the diameter of the NPs and an increase in the effective magnetic anisotropy (Keff) with decreasing particle size. The magnetic moment per particle was calculated for all samples using the susceptibility value at T= 300 K. The number of uncompensated spins per NP was found to be proportional to n1/3S(nS≡ total number of spins), indicating that they are randomly distributed on the NP surface. For small diameters (<30 nm) the surface anisotropy constant was estimated, using, for NiO NPs, a recent model describing the evolution of Keffwith particle size. Hysteretic loops performed at low temperatures after field cooling displayed loop shifts (∼6.5 kOe in the field axis and ∼0.18 emu g−1vertically), coercive field enhancement (HC 4.8 kOe) and training effects for the smaller NPs. The sample with NPs of larger diameters presented magnetic properties close to those of bulk NiO. [ABSTRACT FROM AUTHOR]

The worldwide energy scarcity arising from the massive consumption of nonrenewable energy sources raised a global awareness of the need for cleaner and affordable energy solutions to mitigate climate change and ensure the world sustainable development. The rise of the Internet of Things and the fast growth of the groundbreaking market of wearable electronics boosted a major quest for self-powered technologies merging energy harvesting and energy storage functionalities to meet the demands of a myriad of market segments, such as healthcare, transportation, defense and sports. Thermoelectric devices are a green energy harvesting solution for wearable electronics since they harness the low-grade waste heat from ubiquitous thermal energy sources and convert it into electrical energy. However, these systems generate electrical energy in an intermittent manner, depend on the local heat release availability and require an additional unit to store energy. Flexible and wearable supercapacitors are a safe and eco-friendly energy storage solution to power wearables, offering advantages of security, longer cycle life, higher power density and faster charging over batteries. However, an additional unit that generates energy or that is able to charge the storage device is required. More recently, a new class of all-in-one thermally-chargeable supercapacitors blossomed to meet the requirements of the next generation of autonomous wearable electronics and ensure an endurable energy supply. This self-chargeable hybrid technology combines the functionalities of thermal energy harvesting and supercapacitive energy storage in a single multitasking device. In this Perspective, the advances in the burgeoning field of all-in-one thermally-chargeable supercapacitors for flexible/wearable applications will be critically examined, ranging from their structure and working principle to the rational design of the composing materials and of tailor-made architectures. It will start by introducing the foundations of single flexible/wearable thermoelectric generators and supercapacitors and will evolve into the pioneering venture of fully-integrated thermal energy harvesting/storage systems. It will end by highlighting the current bottlenecks and future pathways for advancing the development of this sophisticated smart technology.

This work reports the mastered design of novel water-dispersible superparamagnetic iron oxide nanomaterials with enhanced magnetic properties and reduced size. A straightforward cost-effective aqueous coprecipitation route was developed, based on the use of three new coprecipitation agents: the polydentate bases diethanolamine, triethanolamine and triisopropanolamine. Through the selection of these alkanolamines which presented different complexing properties, an improvement of the surface spin order could be achieved upon the reduction of the nanomaterial dimensions (from 8.7 to 3.8 nm) owing to the complexation of the polydentate bases with the subcoordinated iron cations on the particle surface. In particular, the alkanolamine with the highest chelating ability (triethanolamine) led to the nanomaterial with the smallest size and the thinnest magnetic "dead" layer. In order to evaluate the importance of the dual control of size and magnetism, the relaxometric properties of the nanomaterials were investigated, whereby maximum values of transverse relaxivity r 2 of 300.30 and 253.92 mM -1 s -1 at 25 and 37 °C, respectively (at 20 MHz) were achieved, making these nanomaterials potential T 2 -weighted MRI contrast agents. Moreover, these values were significantly higher than those reported for commercial T 2 contrast agents and other iron oxides with identical dimensions. Hence, we were able to demonstrate that the r 2 enhancement cannot only be achieved by an increase of particle/cluster size, but also through the precise control of the surface magnetic properties while constraining the nanomaterial dimensions. These achievements open up new perspectives on the mastered design of magnetic nanoprobes, overcoming the limitations related to the deleterious effect of size reduction.

This work reports a detailed investigation about the physicochemical properties of superparamagnetic gamma-Fe(2)O(3) nanomaterial synthesized by the co-precipitation method and coated with two silica shells, and its application as support for the immobilization of oxovanadium(IV) acetylacetonate ([VO(acac)(2)]). The influence of the silica coatings on the surface composition and physicochemical interactions of the core-shell nanocomposites is discussed based on the combination of several techniques: electron microscopy techniques (SEM and TEM with EDS), DLS, powder XRD, XPS, FTIR and magnetic characterization. The identity of the iron oxide, gamma-Fe(2)O(3), was confirmed by XPS, FTIR and by the Rietveld refinement of the PXRD pattern. The results obtained by electron microscopy techniques, XRD and magnetization indicated that the gamma-Fe(2)O(3) nanoparticles are superparamagnetic and present an average size of approximately 6.5 nm. The first silica coating leads to a core-shell nanomaterial with an average particle size of 21 nm and upon the second coating, the average size increases to 240 nm. Magnetic measurements revealed that the silica-coated nanomaterials maintain the superparamagnetic state at room temperature, although with an expected reduction of the magnetization saturation due to the increase of the silica shell thickness. Furthermore, a numerical fit of the temperature dependence of magnetization was performed to determine the core size distribution and the effect of the silica coatings on the dipolar magnetic interactions. [VO(acac)(2)] was covalently immobilized on the surface of the silica-coated magnetic nanoparticles functionalized with amine groups, as confirmed by chemical analysis and XPS. In a proof-of-principle experiment, we demonstrated the catalytic performance of the novel magnetic hybrid nanomaterial in the epoxidation of geraniol, which presented high selectivity towards the 2,3-epoxygeraniol product and easy recovery by magnetic separation.