Solution Processing of Spinel Nickel Cobaltite: Exfoliation Mechanism, Dispersion Stability, and Applications.

The exfoliation of nonlayered materials to mono- or few-layers is of growing interest to realize their full potential for various applications. Nickel cobaltite (NiCo2O4), which has a spinel crystal structure, is one such nonlayered material with unique properties and has been utilized in a wide range of applications. Herein, NiCo2O4 is synthesized from NiCo2- Layered double hydroxides using a topochemical conversion technique. Subsequently, bulk NiCo2O4 is exfoliated into mono- or few-layer nickel cobaltene nanosheets using liquid-phase exfoliation in various low-boiling point solvents. An analytical centrifuge technique is also utilized to understand the solute-solvent interactions by determining their dispersion stability using parameters such as the instability index and sedimentation velocity. Among the studied solvents, water/isopropyl alcohol cosolvent is found to have better dispersion stability. In addition, density functional theory calculations are carried out to understand the exfoliation mechanism. It is found that the surface termination arising from the Co-O bond needs the least energy for exfoliation. Furthermore, the obtained nickel cobaltene nanosheets are utilized as an active material for supercapacitors without any conductive additives or binders. A solid-state symmetric supercapacitor delivers a specific capacitance of 10.2 mF cm-2 with robust stability, retaining ∼98% capacitance after 4000 cycles.

IR regulation through preferential placement of h-BN nanosheets in a polymer network liquid crystal.

Recently, there has been a great deal of interest in devices which effectively shield near-infrared light with an additional feature of external field tunability, particularly for energy-saving applications. This article demonstrates an approach for fabricating a highly efficient near-infrared regulating device based on a polymer network liquid crystal reinforced with nanosheets of hexagonal-boron nitride (BN). The device achieves ∼84% IR scattering capability over a wavelength range of 800-2300 nm, and can also be regulated by an electric field. Interestingly, the observed high IR regulation is despite individual components of the composite being IR transparent, in stark contrast to earlier attempted incorporation of IR-absorbing/scattering particles. Detailed experimental characterization methods including FESEM corroborated with EDS and Raman spectroscopy suggest that the preferential positioning of the BN nanosheets, a consequence of the photo-polymerization process, is responsible for the observed feature. The IR reflectivity/back scattering that is doubled upon incorporation of the nanosheets results in an enhanced convective/radiative heat barrier capability, as evidenced by thermal imaging and significant (2 °C) reduction in ambient temperature upon one-Sun illumination. Numerical simulation results are also found to be in good agreement with the observed enhanced reflectance values for the BN-incorporated case. The presence of BN augments the mechanical rigidity of the system by a factor of 6.8 without compromising on the device operating voltage. The protocol employed is quite general and thus advantageous with far-reaching applications in passive cooling of buildings and structures, in thermal camouflaging, and in overall energy management.

Nanomechanical study of aqueous-processed h-BN reinforced PVA composites.

Hexagonal boron nitride (h-BN) as a filler has significantly improved the mechanical properties of various polymers composites. Among them, polyvinyl alcohol (PVA) is particularly important for its wide range of industrial applications and biocompatibility nature. However, preparing a homogenous composite of h-BN and PVA in water is troublesome as the aqueous processing of h-BN without any additives is challenging. In this context, a pre-processing technique is used to produce an additive-free aqueous dispersion of h-BN. The uniformly dispersed composites are then prepared with different concentrations of h-BN. Free-standing thin films are fabricated using the doctor blade technique, and nanoindentation is employed to understand their deformation behaviour at smaller length scale for better understanding of micro-mechanism involved. Reduced elastic modulus and hardness of 10 wt% h-BN/PVA composite film are enhanced by ∼93% and ∼159%, respectively, compared to pristine PVA. Frequency sweep dynamic mechanical analysis is performed between 1 and 50 Hz, and the elastic properties of composite materials are found to improve significantly upon addition of h-BN nanosheets. Besides, the impact of h-BN incorporation in stress relaxation behaviour and hardness depth profiling are also investigated. The observed improvement in mechanical properties of the composites may be attributed to the uniform distribution of the nanosheets and the strong interfacial interaction between h-BN and PVA, which ensures efficient mechanical stress transfer at the interface.

Solution Processing of Topochemically Converted Layered WO3 for Multifunctional Applications.

Solution processing of nanomaterials is a promising technique for use in various applications owing to its simplicity and scalability. However, the studies on liquid-phase exfoliation (LPE) of tungsten oxide (WO3 ) are limited, unlike others, by a lack of commercial availability of bulk WO3 with layered structures. Herein, a one-step topochemical synthesis approach to obtain bulk layered WO3 from commercially available layered tungsten disulfide (WS2 ) by optimizing various parameters like reaction time and temperature is reported. Detailed microscopic and spectroscopic techniques confirmed the conversion process. Further, LPE was carried out on topochemically converted bulk layered WO3 in 22 different solvents; among the solvents studied, the propan-2-ol/water (1 : 1) co-solvent system appeared to be the best. This indicates that the possible values of surface tension and Hansen solubility parameters for bulk WO3 could be close to that of the co-solvent system. The obtained WO3 dispersions in a low-boiling-point solvent enable thin films of various thickness to be fabricated by using spray coating. The obtained thin films were used as active materials in supercapacitors without any conductive additives/binders and exhibited an areal capacitance of 31.7 mF cm-2 at 5 mV s-1 . Photo-electrochemical measurements revealed that these thin films can also be used as photoanodes for photo-electrochemical water oxidation.

Additive-free Aqueous Dispersions of Two-Dimensional Materials with Glial Cell Compatibility and Enzymatic Degradability.

Water-dispersible two-dimensional (2D) materials are desirable for diverse applications. Aqueous dispersions make processing safer and greener and enable evaluation of these materials on biological and environmental fronts. To evaluate the effects of 2D materials with biological systems, obtaining dispersions without additives is critical and has been a challenge. Herein, a method was developed for obtaining additive-free aqueous dispersions of 2D materials like transition metal dichalcogenides and hexagonal boron nitride (h-BN). The nanosheet dispersions were investigated through spectroscopic and microscopic methods, along with the role of size on stability. The aqueous media enabled investigations on cytocompatibility and enzymatic degradation of molybdenum disulphide (MoS2 ) and h-BN. Cytocompatibility with mixed glial cells was observed up to concentrations of 100 µg mL-1 , suggesting their plausible usage in bioelectronics. Besides, biodegradation using human myeloperoxidase (hMPO) mediated catalysis was investigated through Raman spectroscopy and electron microscopy. The findings suggested that additive-free 2H-MoS2 and h-BN were degradable by hMPO, with 2H-phase exhibiting better resistance to degradation than the 1T-phase, while h-BN exhibited slower degradation. The findings pave a path for incorporating 2D materials in the burgeoning field of transient bioelectronics.