Electrodeposition of nanostructured catalysts for electrochemical energy conversion: Current trends and innovative strategies

This review discusses the latest advances in electrodeposition of nanostructured catalysts for electrochemical energy conversion: fuel cells, water splitting, and carbon dioxide electroreduction. The method excels at preparing efficient and durable nanostructured materials, such as nanoparticles, single atom clusters, hierarchical bifunctional combinations of hydroxides, selenides, phosphides, and so on. Yet, in most cases, chemical composition cannot be decoupled from catalyst morphology. This compromises the rational design of electrodeposition procedures because performance indicators depend on both morphology and surface chemistry. We expect electrodeposition will keep unraveling its potential as the preferred method for electrocatalyst synthesis once a deeper understanding of the electrochemical growth process is combined with complex chemistries to have control of the morphology and the surface composition of complex (bifunctional) electrocatalysts.     

On the potentiality of a cluster-beam source to produce free-standing one-dimensional and two-dimensional FeAg nanostructures: mechanisms underlying their shape genesis

Controlling the morphology and composition of one-dimensional (1D) and two-dimensional (2D) assemblies of matter is essential to design and create nanostructures with exceptional material properties, for applications ranging from nanoelectronics to nanomedicine. Within this latter, a great interest is placed on assembling magnetoplasmonic nanostructures to enable multimodal biosensing and bioimaging for early diagnosis and prognosis of diseases. To date, the synthesis of such complex nanostructures is mostly relying on wet chemistry and templates. Herein, we employed a templateless physical method to generate FeAg-based anisotropic nanostructures, using a modified cluster source. Under tuned experimental conditions, we demonstrated the successful magnetic-assisted assembly of Fe nanoclusters (Fe NCs), to form stable and permanent branched Fe nanorods (Fe NRs), core@shell Fe@Ag-NRs, Fe nanosheets (Fe NSs), and Fe/Ag-NSs. This assembly is driven by the need to reduce their magnetic interaction energy on one hand and their overall surface energy on the other hand. When NCs and NRs are magnetically brought into intimate contact, they undergo a coalescence process, through the interfacial diffusion of the surface atoms, resulting in the formation of 1D and 2D nanostructures. For Fe@Ag NRs, the advantage conferred by the Ag shell is to protect Fe NRs from oxidation and prevent them from aggregation at the same time. The observed contrast reversal in Scanning Electron Microscopy (SEM) images of Fe NRs and Fe NSs is discussed.     

Nanocomposites induced by two-dimensional titanium carbide nanosheets for highly efficient energy storage

Surface group-rich titanium carbide nanosheets (TCNSs) were successfully fabricated by simply etching Ti₃AlC₂ powders and used as dielectric fillers to promote the dielectric and energy storage performances of poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)-based composites. The PVDF-HFP/TCNS composites realize a high dielectric constant and low dielectric loss of 16.3 and 0.034 at 10² Hz, respectively. Importantly, a high energy storage density (U_e) of 0.367 J cm⁻³ at 900 kV cm⁻¹ and a high energy storage efficiency (η ≥ 78.9%) at a TCNS content of only 0.5 wt% are obtained, which indicates that incorporating TCNS is an efficient route in enhancing U_e while maintaining a high level η of the PVDF-HFP-based composites. According to detailed characterization results, a mechanism related to the reduction of lamellar crystals in the PVDF-HFP matrix is suggested. The above mechanism restricts the movement of polymer chains near the filler-matrix interface and is proposed to be responsible for the outstanding dielectric and energy storage performances. Consequently, this work provides a simple and effective method for fabricating highly efficient energy storage nanocomposites.     

Preparation and formaldehyde sensitive properties of N-GQDs/SnO2 nanocomposite

Graphene quantum dots (GQDs) have both the properties of graphene and semiconductor quantum dots, and exhibit stronger quantum confinement effect and boundary effect than graphene. In addition, the band gap of GQDs will transform to non-zero from 0 eV of graphene by surface functionalization, which can be dispersed in common solvents and compounded with solid materials. In this work, the SnO₂ nanosheets were prepared by hydrothermal method. As the sensitizer, nitrogen-doped graphene quantum dots (N-GQDs) were prepared and composited with SnO₂ nanosheets. Sensing performance of pristine SnO₂ and N-GQDs/SnO₂ were investigated with HCHO as the target gas. The response (R_a/R_g) of 0.1% N-GQDs/SnO₂ was 256 for 100 ppm HCHO at 60 °C, which was about 2.2 times higher than pristine SnO₂ nanosheet. In addition, the material also had excellent selectivity and low operation temperature. The high sensitivity of N-GQDs/SnO₂ was attributed to the increase of active sites on materials surface and the electrical regulation of N-GQDs. This research is helpful to develop new HCHO gas sensor and expand the application field of GQDs.     

Trends in nanomaterial-based solid-phase microextraction with a focus on environmental applications - A review

Effective solid-phase microextraction (SPME) in environmental field represents a crucial step for the adequate extraction of several analytes. Several materials have been traditionally developed for SPME of several analytes from environmental samples, even though their several restrictions such as post-treatment required, elevate costs and limited efficiency. Recently, nanomaterials (NMs) have emerged as a promising substitute for SPME in environmental applications of traditional techniques, due to their small size and their high specific surface-area which enhances their high reactivity. In this present review different NMs which have recently been utilized as SPME sorbent for environmental applications are classified into eleven main groups, namely nanoparticles, nanofibers, nanoflakes, nanocomposites, nanorods, nanotubes, nanohorns, nanosheets, nanocubes, nanospheres and polymer-based NMs. Application of these NMs in SPME modes and configurations for environmental analysis has been reviewed. The study discusses not only the advantages but also the major limitations of using such NMs.     

The bond force constants and elastic properties of boron nitride nanosheets and nanoribbons using a hierarchical modeling approach

A hierarchical approach bridging the atomistic and nanometric scales is used to compute the elastic properties of boron nitride nanosheets and nanoribbons, examining the effect of sheet size, aspect ratio and anisotropy. The approach consists in obtaining the bond force (force field) constants by dedicated computations based on density functional theory (DFT) and using such constants as input for larger scale structural models solved by finite element analysis (FEA). The bond force constants calculated by DFT are 616.9 N/m for stretching, 6.27×10⁻¹⁹ Nm/rad² for in-plane rotation and 1.32×10⁻¹⁹ Nm/rad² for dihedral rotation. Using these constants, the elastic properties of boron nitride nanosheets and nanoribbons predicted by FEA are almost independent of the sheet size, but strongly dependent on their aspect ratio. The sheet anisotropy increases with increased aspect ratio, with nanoribbons of aspect ratios of 10 exhibiting a ratio of elastic moduli along both in-plane directions of 1.7.     

原位核磁共振技术考察L-缬氨酸导引下合成花状纳米结构聚苯胺形成机理的研究

利用~1H-NMR原位追踪在L-缬氨酸存在下合成花状纳米聚苯胺的形成过程中发现此结构的形成经历3个阶段:首先在苯胺与缬氨酸构成的类胶束结构内聚合成吩嗪类寡聚物;其次通过p-p重叠作用及胶束融合过程成为片状聚集体;最终通过与缬氨酸形成氢键组装成花瓣状纳米聚苯胺.通过改变反应条件,对比形成过程中核磁共振图谱及产物形貌的变化发现花状纳米聚苯胺的形成有如下特征:反应初期L-缬氨酸作为缓冲试剂可以避免苯胺的骤然质子化,有利于生成具有吩嗪结构的寡聚物;反应前苯胺单体与缬氨酸形成稳定的反应环境保证寡聚物始终在其内聚集生长,有效避免了外部环境的影响.     

K4Nb6O17-derived photocatalysts for hydrogen evolution from water: Nanoscrolls versus nanosheets

The layered hexaniobate K₄Nb₆O₁₇ is known as a photocatalyst for methanol dehydrogenation and hydrogen evolution from water under ultraviolet (UV) light. Here we show that the activity is retained in propylammonium- (PA) or tetrabutylammonium- (TBA) stabilized H₂K₂Nb₆O₁₇ nanosheets and TBA-stabilized H₄Nb₆O₁₇ nanoscrolls that can be obtained by exfoliation of K₄Nb₆O₁₇ followed by cation exchange. The catalytic activity of the exfoliated systems is comparable to K₄Nb₆O₁₇, with scrolls being most active in water, and PA sheets giving enhanced H₂ rates due to sacrificial electron donor action of PA. Femtosecond absorption spectra for TBA scrolls and PA sheets exhibit broad features between 450 and 700 nm due to trapped holes and electrons. Electron–hole recombination follows approximately second-order kinetics, with rates of decay similar for sheets and scrolls. In addition, catalysts were characterized with UV/vis and fluorescence spectroscopy and transmission electron microscopy.     

Controlled synthesis of ZnO with adjustable morphologies from nanosheets to microspheres

The synthesis of ZnO with different morphologies (hexagonal prisms, nanosheets, microspheres and quasi-flowers) was realized through a solvothermal method. During the synthetic procedure, the decomposition of hexamethylenetetramine at the temperature ≥100 °C provided (OH)⁻¹ ions at the rate of good distribution, and sodium dodecyl sulfate was used as templates. By adjusting the basicity in the synthetic system, ZnO nanosheets, or microspheres with nanosheet assemblies were obtained. Adjusting the concentration of surfactant, ZnO hexagonal crystals were formed; by adjusting the synthetic temperature, ZnO quasi-flowers with some nanosheet assemblies were produced. Based on experimental observation and analysis, the forming mechanism was discussed.     

High-sensitivity determination of lead and cadmium based on the Nafion-graphene composite film

Graphene nanosheets, dispersed in Nafion (Nafion-G) solution, were used in combination with in situ plated bismuth film electrode for fabricating the enhanced electrochemical sensing platform to determine the lead (Pb²⁺) and cadmium (Cd²⁺) by differential pulse anodic stripping voltammetry (DPASV). The electrochemical properties of the composite film modified glassy carbon electrode were investigated. It is found that the prepared Nafion-G composite film not only exhibited improved sensitivity for the metal ion detections, but also alleviated the interferences due to the synergistic effect of graphene nanosheets and Nafion. The linear calibration curves ranged from 0.5 μg L⁻¹ to 50 μg L⁻¹ for Pb²⁺ and 1.5 μg L⁻¹ to 30 μg L⁻¹ for Cd²⁺, respectively. The detection limits (S/N = 3) were estimated to be around 0.02 μg L⁻¹ for Pb²⁺ and Cd²⁺. The practical application of the proposed method was verified in the water sample determination.