Nanomaterials

In recent years, metal–organic gels (MOGs) have attracted much attention due to their hierarchical porous structure, large specific surface area, and good surface modifiability. Compared with MOFs, the synthesis conditions of MOGs are gentler and more stable. At present, MOGs are widely used in the fields of catalysis, adsorption, energy storage, electrochromic devices, sensing, analysis, and detection. In this paper, literature metrology and knowledge graph visualization analysis are adopted to analyze and summarize the literature data in the field of MOGs. The visualization maps of the temporal distribution, spatial distribution, authors and institutions’ distribution, influence of highly cited literature and journals, keyword clustering, and research trends are helpful to clearly grasp the content and development trend of MOG materials research, point out the future research direction for scholars, and promote the practical application of MOGs. At the same time, the paper reviews the research and application progress of MOGs in recent years by combining keyword clustering, time lines, and emergence maps, and looks forward to their challenges, future development trend, and application prospects. Full article

This work investigates the optical properties of Yb³⁺ ions doped GeO₂-PbO glasses containing Ag nanoclusters (NCs), produced by the melt-quenching technique. The lack in the literature regarding the energy transfer (ET) between these species in these glasses motivated the present work. Tunable visible emission occurs from blue to orange depending on the Yb³⁺ concentration which affects the size of the Ag NCs, as observed by transmission electron microscopy. The ET mechanism from Ag NCs to Yb³⁺ ions (²F_7/2 → ²F_5/2) was attributed to the S₁→T₁ decay (spin-forbidden electronic transition between singlet–triplet states) and was corroborated by fast and slow lifetime decrease (at 550 nm) of Ag NCs and photoluminescence (PL) growth at 980 nm, for excitations at 355 and 405 nm. The sample with the highest Yb³⁺ concentration exhibits the highest PL growth under 355 nm excitation, whereas at 410 nm it is the sample with the lowest concentration. The restriction of Yb³⁺ ions to the growth of NCs is responsible for these effects. Thus, higher Yb³⁺ concentration forms smaller Ag NCs, whose excitation at 355 nm leads to more efficient ET to Yb³⁺ ions compared to 410 nm. These findings have potential applications in the visible to near-infrared regions, such as tunable CW laser sources and photovoltaic devices. Full article

Designing and preparing dual-functional Dawson-type polyoxometalate-based metal–organic framework (POMOF) energy storage materials is challenging. Here, the Dawson-type POMOF nanomaterial with the molecular formula CoK₄[P₂W₁₈O₆₂]@Co₃(btc)₂ (abbreviated as {P₂W₁₈}@Co-BTC, H₃btc = 1,3,5-benzylcarboxylic acid) was prepared using a solid-phase grinding method. XRD, SEM, TEM et al. analyses prove that this nanomaterial has a core–shell structure of Co-BTC wrapping around the {P₂W₁₈}. In the three-electrode system, it was found that {P₂W₁₈}@Co-BTC has the best supercapacitance performance, with a specific capacitance of 490.7 F g⁻¹ (1 A g⁻¹) and good stability, compared to nanomaterials synthesized with different feedstock ratios and two precursors. In the symmetrical double-electrode system, both the power density (800.00 W kg⁻¹) and the energy density (11.36 Wh kg⁻¹) are greater. In addition, as the electrode material for the H₂O₂ sensor, {P₂W₁₈}@Co-BTC also exhibits a better H₂O₂-sensing performance, such as a wide linear range (1.9 μM–1.67 mM), low detection limit (0.633 μM), high selectivity, stability (92.4%) and high recovery for the detection of H₂O₂ in human serum samples. This study provides a new strategy for the development of Dawson-type POMOF nanomaterial compounds. Full article

Artificial nanostructures with large optical chiral responses have been intensively investigated recently. In this work, we propose a diffractive circular dichroism enhancement technique using stereoscopic plasmonic molecule structures. According to the multipole expansion analysis, the z-component of the electric dipole becomes the dominant chiral scattering mechanism during the interaction between an individual plasmonic molecule and the plane wave at a grazing angle. For a periodical structure with the designed plasmonic molecule, large diffractive circular dichroism can be obtained, which can be associated with the Wood–Rayleigh anomaly. Such a diffractive circular dichroism enhancement is verified by the good agreement between numerical simulations and experimental results. The proposed approach can be potentially used to develop enhanced spectroscopy techniques to measure chiral information, which is very important for fundamental physical and chemical research and bio-sensing applications. Full article

Titanium dioxide nanoparticles (TiO₂ NPs) are one of the main sources of the nanoparticulate matter exposure to humans. Although several studies have demonstrated their potential toxic effects, the real nature of the correlation between NP properties and their interaction with biological targets is still far from being fully elucidated. Here, engineered TiO₂ NPs with various geometries (bipyramids, plates, and rods) have been prepared, characterized and intravenously administered in healthy mice. Parameters such as biodistribution, accumulation, and toxicity have been assessed in the lungs and liver. Our data show that the organ accumulation of TiO₂ NPs, measured by ICP-MS, is quite low, and this is only partially and transiently affected by the NP geometries. The long-lasting permanence is exclusively restricted to the lungs. Here, bipyramids and plates show a higher accumulation, and interestingly, rod-shaped NPs are the most toxic, leading to histopathological pulmonary alterations. In addition, they are also able to induce a transient increase in serum markers related to hepatocellular injury. These results indicate that rods, more than bipyramidal and spherical geometries, lead to a stronger and more severe biological effect. Overall, small physico-chemical differences can dramatically modify both accumulation and safety. Full article

We have investigated platinum catalysts containing iron as a modifier to obtain catalysts with superior electrocatalytic activity toward glycerol electro-oxidation in an alkaline medium. The electrocatalysts, supported on carbon Vulcan, were synthesized by the polyol method. The physicochemical characterization data showed that the metals were well distributed on the carbon support and had small particle size (2 nm). The Pt:Fe metal ratio differed from the nominal composition, indicating that reducing iron with platinum was difficult, even though some parameters of the synthesis process were changed. Electrochemical analyses revealed that PtFe/C was more active and stable than commercial Pt/C was, and analysis of the electrolysis by-products showed that iron addition to Pt/C boosted the glycerol conversion and selectivity for glyceric acid formation. Full article

Layered magnetic metal-organic frameworks (MOFs) are an emerging class of materials that can combine the advantages of both MOFs and 2D magnetic crystals. The recent discovery of large coercivity and long-range magnetic ordering up to 515 K in a layered MOF of general formula MCl₂(pyz)₂ (M = transition metal, pyz = pyrazine) offers an exciting versatile platform to achieve high-T_C magnetism at the 2D limit. In this work, we investigate the exfoliation feasibility down to the monolayer of VCl₂(pyz)₂ and CrCl₂(pyz)₂ by means of first-principles calculations. We explore their structural, electronic, magnetic and vibrational properties, as well as the effect of halide substitution. Then, we provide a full analysis of the spin-phonon coupling (SPC) in both 2D derivatives. Our calculations reveal a low SPC and thermal evolution of the magnetic exchange interactions and single-ion anisotropy mainly governed by low-frequency phonon modes. Finally, we provide chemical insights to improve the performance of these magnetic 2D MOFs based on the effective manipulation of the phonon modes that can present a major impact on their magnetic properties. Full article

Indium oxide (In₂O₃) is a widely used n-type semiconductor for detection of pollutant gases; however, its gas selectivity and sensitivity have been suboptimal in previous studies. In this work, zinc-doped indium oxide nanowires with appropriate morphologies and high crystallinity were synthesized using chemical vapor deposition (CVD). An accurate method for electrical measurement was attained using a single nanowire microdevice, showing that electrical resistivity increased after doping with zinc. This is attributed to the lower valence of the dopant, which acts as an acceptor, leading to the decrease in electrical conductivity. X-ray photoelectron spectroscopy (XPS) analysis confirms the increased oxygen vacancies due to doping a suitable number of atoms, which altered oxygen adsorption on the nanowires and contributed to improved gas sensing performance. The sensing performance was evaluated using reducing gases, including carbon monoxide, acetone, and ethanol. Overall, the response of the doped nanowires was found to be higher than that of undoped nanowires at a low concentration (5 ppm) and low operating temperatures. At 300 °C, the gas sensing response of zinc-doped In₂O₃ nanowires was 13 times higher than that of undoped In₂O₃ nanowires. The study concludes that higher zinc doping concentration in In₂O₃ nanowires improves gas sensing properties by increasing oxygen vacancies after doping and enhancing gas molecule adsorption. With better response to reducing gases, zinc-doped In₂O₃ nanowires will be applicable in environmental detection and life science. Full article

An infrared photodetector is a critical component that detects, identifies, and tracks complex targets in a detection system. Infrared photodetectors based on 3D bulk materials are widely applied in national defense, military, communications, and astronomy fields. The complex application environment requires higher performance and multi-dimensional capability. The emergence of 2D materials has brought new possibilities to develop next-generation infrared detectors. However, the inherent thickness limitations and the immature preparation of 2D materials still lead to low quantum efficiency and slow response speeds. This review summarizes 2D/3D hybrid van der Waals heterojunctions for infrared photodetection. First, the physical properties of 2D and 3D materials related to detection capability, including thickness, band gap, absorption band, quantum efficiency, and carrier mobility, are summarized. Then, the primary research progress of 2D/3D infrared detectors is reviewed from performance improvement (broadband, high-responsivity, fast response) and new functional devices (two-color detectors, polarization detectors). Importantly, combining low-doped 3D and flexible 2D materials can effectively improve the responsivity and detection speed due to a significant depletion region width. Furthermore, combining the anisotropic 2D lattice structure and high absorbance of 3D materials provides a new strategy in high-performance polarization detectors. This paper offers prospects for developing 2D/3D high-performance infrared detection technology. Full article

Stimulated Raman scattering in transparent glass-ceramics (TGCs) based on bulk nucleating phase Ba₂NaNb₅O₁₅ were investigated with the aim to explore the influence of micro- and nanoscale structural transformations on Raman gain. Nanostructured TGCs were synthesized, starting with 8BaO·15Na₂O·27Nb₂O₅·50SiO₂ (BaNaNS) glass, by proper nucleation and crystallization heat treatments. TGCs are composed of nanocrystals that are 10–15 nm in size, uniformly distributed in the residual glass matrix, with a crystallinity degree ranging from 30 up to 50% for samples subjected to different heat treatments. A significant Raman gain improvement for both BaNaNS glass and TGCs with respect to SiO₂ glass is demonstrated, which can be clearly related to the nanostructuring process. These findings show that the nonlinear optical functionalities of TGC materials can be modulated by controlling the structural transformations at the nanoscale rather than microscale. Full article

A new low-cost material with a polymeric base formed from sodium silicate was developed. The material presents a nanostructured, highly rich iron surface with a large phosphorus retention capacity and potential reuse as a crop fertilizer. In the present study, we demonstrate that iron is the element that acts as an adsorbent for phosphate, while the polymeric base functions exclusively as a support for iron. The iron is uniformly adsorbed on the surface of the material, forming nanostructures, which ensure that iron works similarly to nanoparticles in solution but avoid other problems, such as particle agglomeration or the difficulty of separating them after the removal process. Materials were characterised by SEM, EDS, N₂ sorption, and image processing, and the effect of pH, ionic strength, and temperature was studied. Sorption kinetics were analysed using Boyd’s diffusion model, and adsorption equilibria were studied using several adsorption models. A maximum iron adsorption on the polymeric base of 23.9 ± 0.3 mg Fe∙g⁻¹ was found, while maximum phosphorus adsorption was 366 ± 21 mg P∙g⁻¹ Fe. Thus, phosphorus is recovered from the aqueous medium with an inexpensive material that has the potential to be used directly as a fertilizer. Full article

The world scenario has undergone a nutritional transition in which some countries have left the reality of malnutrition and now face an epidemic of excess body weight. Researchers have been looking for strategies to reverse this situation. Peptides and proteins stand out as promising molecules with anti-obesity action. However, oral administration and passage through the gastrointestinal tract face numerous physiological barriers that impair their bioactive function. Encapsulation aims to protect the active substance and modify the action, one possibility of potentiating anti-obesity activity. Research with encapsulated peptides and proteins has demonstrated improved stability, delivery, controlled release, and increased bioactivity. However, it is necessary to explore how proteins and peptides affect weight loss and satiety, can impact the nutritional status of obesity, and how encapsulation can enhance the bioactive effects of these molecules. This integrative review aimed to discuss how the encapsulation of protein molecules impacts the nutritional status of obesity. From the studies selected following pre-established criteria, it was possible to infer that the encapsulation of proteins and peptides can contribute to greater efficiency in reducing weight gain, changes in adipose tissue function, and lower hormone levels that modulate appetite and body weight in animals with obesity. Full article

The stoichiometric compositions of a ferrite system with a chemical formula CoCr_0.5Dy_xFe_1.5-xO₄ where x = 0.0, 0.025, 0.05, 0.075 and 0.1 were prepared by the sol-gel auto-combustion method. The structural, morphological and magnetic properties were studied by the X-ray diffraction (XRD), infra-red spectroscopy (IR), scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer. XRD analysis confirmed the cubic spinel structure of the prepared samples without the presence of any impurity and secondary phases. Selected area electron diffraction and IR measurements gives further confirmation to the XRD observations. Considering that strain mechanism, elastic properties and cation distribution play a major role for controlling the magnetic properties and therefore these properties were precisely evaluated through reliable methodologies such as XRD and IR data. The cation distribution was determined by the X-ray diffraction data which are further supported by the magnetization studies. Magnetoelectric properties of CoCr_0.5Dy_xFe_1.5−xO₄ + BaTiO₃ have also been investigated. The mechanisms involved are discussed in the manuscript. Full article

The first report of deep eutectic solvents (DESs) was released in 2003 and was identified as a new member of ionic liquid (IL), involving innovative chemical and physical characteristics. Using green solvent technology concerning economical, practical, and environmental aspects, DESs open the window for sustainable development of nanomaterial fabrication. The DESs assist in different fabrication processes and design nanostructures with specific morphology and properties by tunable reaction conditions. Using DESs in synthesis reactions can reduce the required high temperature and pressure conditions for decreasing energy consumption and the risk of environmental contamination. This review paper provides the recent applications and advances in the design strategy of DESs for the green synthesis of nanomaterials. The strategy and application of DESs in wet-chemical processes, nanosize reticular material fabrication, electrodeposition/electrochemical synthesis of nanostructures, electroless deposition, DESs based nano-catalytic and nanofluidic systems are discussed and highlighted in this review. Full article

Non-enzymatic electrochemical glucose sensors are of great importance in biomedical applications, for the realization of portable diabetic testing kits and continuous glucose monitoring systems. Nanostructured materials show a number of advantages in the applications of analytical electrochemistry, compared to macroscopic electrodes, such as great sensitivity and little dependence on analyte diffusion close to the electrode–solution interface. Obtaining electrodes based on nanomaterials without using expensive lithographic techniques represents a great added value. In this paper, we modeled the chronoamperometric response towards glucose determination by four electrodes consisting of nanostructured gold onto graphene paper (GP). The nanostructures were obtained by electrochemical etch, thermal and laser processes of thin gold layer. We addressed experiments obtaining different size and shape of gold nanostructures. Electrodes have been characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, and chronoamperometry. We modeled the current-time response at the potential corresponding to two-electrons oxidation process of glucose by the different nanostructured gold systems. The finest nanostructures of 10–200 nm were obtained by laser dewetting of 17 nm thin and 300 °C thermal dewetting of 8 nm thin gold layers, and they show that semi-infinite linear diffusion mechanism predominates over radial diffusion. Electrochemical etching and 17 nm thin gold layer dewetted at 400 °C consist of larger gold islands up to 1 μm. In the latter case, the current-time curves can be fitted by a two-phase exponential decay function that relies on the mixed second-order formation of adsorbed glucose intermediate followed by its first-order decay to gluconolactone. Full article

Halloysite particles, with their unique multilayer nanostructure, are demonstrated here as highly efficient and readily available sorbent of heavy metals that can be easily scaled up and used in large-scale water remediation facilities. The various methods of raw material purification were applied, and their effects were verified using techniques such as BET isotherm (determination of specific surface area and size of pores), XRF analysis (composition), and SEM imaging (determination of morphology). A series of adsorption experiments for aqueous solutions of metal ions (i.e., lead, cadmium) were carried out to quantify the sorption capacity of halloysite particles for selected heavy metals. The ability of adequately activated halloysite to efficiently remove heavy metal ions from water solutions was confirmed. The value of the zeta potential of raw and purified halloysite particles in water was determined. This enables us to understand its importance for the sorption of positively charged ions (metal, organics) at various pH values. The adsorption process conducted in the pH range of 6.0–6.5 showed significant improvement compared to the acidic conditions (pH value 3.0–3.5) and resulted in a high sorption capacity of lead ions—above 24.3 mg/g for the sulphuric acid-treated sample. The atomic scale ab initio calculations revealed a significant difference in adsorption energy between the external siloxane surface and cross-sectional interlayer surface, resulting in pronounced adsorption anisotropy. A low energy barrier was calculated for the interlayer migration of heavy metals into the halloysite interior, facilitating access to the active sites in these regions, thus significantly increasing the sorption capacity and kinetics. DFT (density functional theory) calculations supporting this study allowed for predicting the sorption potential of pure halloysite structure towards heavy metals. To confront it with experimental results, it was crucial to determine proper purification conditions to obtain such a developed structure from the mineral ore. The results show a massive increase in the BET area and confirm a high sorption potential of modified halloysite towards heavy metals. Full article

A novel composite hydrogel bead composed of sodium alginate (SA) and aldehyde cellulose nanocrystal (DCNC) was developed for antibiotic remediation through a one-step cross-linking process in a calcium chloride bath. Structural and physical properties of the hydrogel bead, with varying composition ratios, were analyzed using techniques such as BET analysis, SEM imaging, tensile testing, and rheology measurement. The optimal composition ratio was found to be 40% (SA) and 60% (DCNC) by weight. The performance of the SA–DCNC hydrogel bead for antibiotic remediation was evaluated using doxycycline (DOXY) and three other tetracyclines in both single- and multidrug systems, yielding a maximum adsorption capacity of 421.5 mg g⁻¹ at pH 7 and 649.9 mg g⁻¹ at pH 11 for DOXY. The adsorption mechanisms were investigated through adsorption studies focusing on the effects of contact time, pH, concentration, and competitive contaminants, along with X-ray photoelectron spectroscopy analysis of samples. The adsorption of DOXY was confirmed to be the synergetic effects of chemical reaction, electrostatic interaction, hydrogen bonding, and pore diffusion/surface deposition. The SA–DCNC composite hydrogel demonstrated high reusability, with more than 80% of its adsorption efficiency remaining after five cycles of the adsorption–desorption test. The SA–DCNC composite hydrogel bead could be a promising biomaterial for future antibiotic remediation applications in both pilot and industrial scales because of its high adsorption efficiency and ease of recycling. Full article

ZnS–graphene composites (ZnSGO) were synthesized by a hydrothermal process and loaded onto carbon nanofibers (CNFs) by electrospinning (ZnS–GO/CNF), to obtain self-standing anodes for SIBs. The characterization techniques (XRPD, SEM, TEM, EDS, TGA, and Raman spectroscopy) confirm that the ZnS nanocrystals (10 nm) with sphalerite structure covered by the graphene sheets were successfully synthesized. In the ZnS–GO/CNF anodes, the active material is homogeneously dispersed in the CNFs’ matrix and the ordered carbon source mainly resides in the graphene component. Two self-standing ZnS–GO/CNF anodes (active material amount: 11.3 and 24.9 wt%) were electrochemically tested and compared to a tape-casted ZnS–GO example prepared by conventional methods (active material amount: 70 wt%). The results demonstrate improved specific capacity at high C-rate for the free-standing anodes compared to the tape-casted example (69.93 and 92.59 mAh g⁻¹ at 5 C for 11.3 and 24.9 wt% free-standing anodes, respectively, vs. 50 mAh g⁻¹ for tape-casted). The 24.9 wt% ZnS–GO/CNF anode gives the best cycling performances: we obtained capacities of 255–400 mAh g⁻¹ for 200 cycles and coulombic efficiencies ≥ 99% at 0.5 C, and of 80–90 mAh g⁻¹ for additional 50 cycles at 5 C. The results suggest that self-standing electrodes with improved electrochemical performances at high C-rates can be prepared by a feasible and simple strategy: ex situ synthesis of the active material and addition to the carbon precursor for electrospinning. Full article