Interfacial Coupling of Graphene with Nickel Nanoparticles for Water Splitting and Urea Oxidation: A Spectroelectrochemical Investigation.

Nickel nanoparticle and graphene interfaces of various stoichiometries were created through electrodeposition techniques. The catalytic behavior of the electrodeposited films was investigated through spectro-electrochemical methodologies. UV-vis absorbance spectra of the electrodeposited films are significantly different in the air and alkaline medium. Furthermore, UV-vis and Raman spectroscopy confirmed the coupling of Ni nanoparticles (Ni-NP) with the graphene framework, along with NiO and Ni(OH)2 . A combination of Raman and impedance spectroscopy revealed that the surface adsorption and charge transfer properties of the electrodeposited films are entirely dependent on the defects on graphene structure as well as distribution of Ni-NP on graphene. The electrodeposited films possess heterogeneous catalytic properties with a low overpotential of 50 mV (10 mA/cm-2 ) for hydrogen evolution reaction, as well as 601 mV and 391 mV (at 50 mA/cm-2 ) for the oxygen evolution reaction and urea oxidation reaction, respectively. In addition, eelectrodeposited samples show extraordinary overall water splitting performance by achieving a current density of 10 mA/cm2 at a very low applied potential of 1.38 V. This synergistic coupling of Ni and graphene renders the electrodeposited samples promising candidates as electrodes for overall water splitting in alkaline and urea-supplemented solutions.

Water-dispersible Ti3C2Tz MXene nanosheets by molten salt etching.

Molten-salt etching of Ti3AlC2 MAX phase offers a promising route to produce 2D Ti3C2Tz (MXene) nanosheets without hazardous HF. However, molten-salt etching results in MXene clays that are not water dispersible, thus preventing further processing. This occurs because molten-salt etching results in a lack of -OH terminal groups rendering the MXene clay hydrophobic. Here, we demonstrate a method that produces water-dispersible Ti3C2Tz nanosheets using molten salt (SnF2) to etch. In molten salt etching, SnF2 diffuses between the layers to form AlF3 and Sn as byproducts, separating the layers. The stable, aqueous Ti3C2Tz dispersion yields a ζ potential of -31.7 mV, because of -OH terminal groups introduced by KOH washing. X-ray diffraction and electron microscopy confirm the formation of Ti3C2Tz etched clay with substantial d-spacing as compared with clay etched with HF. This work is the first to use molten salt etching to successfully prepare colloidally stable aqueous dispersions of Ti3C2Tz nanosheets.

One-step hydrothermal synthesis of porous Ti3C2Tz MXene/rGO gels for supercapacitor applications.

Titanium carbide/reduced graphene oxide (Ti3C2Tz/rGO) gels were prepared by a one-step hydrothermal process. The gels show a highly porous structure with a surface area of ∼224 m2 g-1 and average pore diameter of ∼3.6 nm. The content of GO and Ti3C2Tz nanosheets in the reaction precursor was varied to yield different microstructures. The supercapacitor performance of Ti3C2Tz/rGO gels varied significantly with composition. Specific capacitance initially increased with increasing Ti3C2Tz content, but at high Ti3C2Tz content gels cannot be formed. Also, the retention of capacitance decreased with increasing Ti3C2Tz content. Ti3C2Tz/rGO gel electrodes exhibit enhanced supercapacitor properties with high potential window (1.5 V) and large specific capacitance (920 F g-1) in comparison to pure rGO and Ti3C2Tz. The synergistic effect of EDLC from rGO and redox capacitance from Ti3C2Tz was the reason for the enhanced supercapacitor performance. A symmetric two-electrode supercapacitor cell was constructed with Ti3C2Tz/rGO, which showed very high areal capacitance (158 mF cm-2), large energy density (∼31.5 µW h cm-2 corresponding to a power density of ∼370 µW cm-2), and long stability (∼93% retention) after 10 000 cycles.

Investigation of the surface plasmon polariton and electrochemical properties of covalent and non-covalent functionalized reduced graphene oxide.

The surface electronic properties of graphene oxide (GO) were modified through reduction and functionalization. Non-covalent functionalization was found to be superior compared to covalent functionalization due to the formation of few-layer graphene with a low defect content and average crystalline length. Because of the restoration of sp2 hybridization, non-covalently functionalized reduced graphene oxide (rGO) showed a better plasmonic response compared to GO, rGO and covalently functionalized rGO. Due to the available π electrons from the sp2 network of graphene as well as surface functionality, non-covalent functionalized rGO exhibited elevated donor density. Furthermore, due to the synergistic effect of surface electronic properties as well as adsorption and recombination at the barrier, superior charge transfer was achieved at the electrode-electrolyte interface for non-covalent functionalized rGO.

Band Gap Engineering of Boron Nitride by Graphene and Its Application as Positive Electrode Material in Asymmetric Supercapacitor Device.

Nanostructured hexagonal boron nitride (h-BN)/reduced graphene oxide (RGO) composite is prepared by insertion of h-BN into the graphene oxide through hydrothermal reaction. Formation of the super lattice is confirmed by the existence of two separate UV-visible absorption edges corresponding to two different band gaps. The composite materials show enhanced electrical conductivity as compared to the bulk h-BN. A high specific capacitance of ∼824 F g(-1) is achieved at a current density of 4 A g(-1) for the composite in three-electrode electrochemical measurement. The potential window of the composite electrode lies in the range from -0.1 to 0.5 V in 6 M aqueous KOH electrolyte. The operating voltage is increased to 1.4 V in asymmetric supercapacitor (ASC) device where the thermally reduced graphene oxide is used as the negative electrode and the h-BN/RGO composite as the positive electrode. The ASC exhibits a specific capacitance of 145.7 F g(-1) at a current density of 6 A g(-1) and high energy density of 39.6 W h kg(-1) corresponding to a large power density of ∼4200 W kg(-1). Therefore, a facile hydrothermal route is demonstrated for the first time to utilize h-BN-based composite materials as energy storage electrode materials for supercapacitor applications.

Development of high energy density supercapacitor through hydrothermal synthesis of RGO/nano-structured cobalt sulphide composites.

Co9S8/reduced graphene oxide (RGO) composites were prepared on nickel foam substrate through hydrothermal reaction and used directly as supercapacitor electrode. The field emission scanning electron microscopy analysis of the composites showed the formation of Co9S8 nano-rods on the RGO surfaces. The average crystal size of the Co9S8 nano rods grown on the RGO sheets were ∼25-36 nm as calculated from x-ray diffraction analysis. The reduction of graphene oxide (GO) was confirmed by Raman and x-ray photoelectron spectroscopy analysis. The electrical conductivity of the Co9S8/RGO composite was recorded as 1690 S m(-1) at room temperature, which is much higher than that of pure GO further confirming the hydrothermal reduction of GO. Cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy were investigated to check the electrochemical performances of the Co9S8/RGO composites. The Co9S8/RGO composites supported on nickel foam showed very high specific capacitance (Sc)(1349 F g(-1) at a current density of 2.2 A g(-1)), energy density (68.6 W h kg(-1)) and power density (1319 W kg(-1)) in 6 M KOH electrolyte. The retention in Sc of the composite electrode was found to be ∼96% after 1000 charge-discharge cycles.