Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm -1 of GO to 1585 cm -1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.
Electrochemical capacitors are electrochemical devices with fast and highly reversible charge-storage and discharge capabilities. The devices are attractive for energy storage particularly in applications involving high-power requirements. Electrochemical capacitors employ two electrodes and an aqueous or a non-aqueous electrolyte, either in liquid or solid form; the latter provides the advantages of compactness, reliability, freedom from leakage of any liquid component and a large operating potential-window. One of the classes of solid electrolytes used in capacitors is polymer-based and they generally consist of dry solid-polymer electrolytes or gel-polymer electrolyte or composite-polymer electrolytes. Dry solid-polymer electrolytes suffer from poor ionic-conductivity values, between 10 À8 and 10 À7 S cm À1 under ambient conditions, but are safer than gel-polymer electrolytes that exhibit high conductivity of ca. 10 À3 S cm À1 under ambient conditions. The aforesaid polymer-based electrolytes have the advantages of a wide potential window of ca. 4 V and hence can provide high energy-density. Gel-polymer electrolytes are generally prepared using organic solvents that are environmentally malignant. Hence, replacement of organic solvents with water in gel-polymer electrolytes is desirable which also minimizes the device cost substantially. The water containing gel-polymer electrolytes, called hydrogel-polymer electrolytes, are, however, limited by a low operating potential-window of only about 1.23 V. This article reviews salient features of electrochemical capacitors employing hydrogel-polymer electrolytes.
The subject of sol-gel electrochemistry is introduced, starting with a brief account of milestones in its evolution. Then, the types of sol-gel materials that are useful for electrochemistry are presented, followed by a description of recent advances in the various fields of sol-gel electrochemistry. Modified electrodes, solid electrolytes, electrochromic devices, and corrosion protection coatings are described. Emerging fields such as RuO 2 supercapacitors and electrochemical synthesis of sol-gel precursors are also addressed.
Few-layer transition metal dichalcogenide alloys based on molybdenum sulphoselenides [MoS2(1-x)Se2x] possess higher hydrogen evolution (HER) activity compared to pristine few-layer MoS2 and MoSe2. Variation of the sulphur or selenium content in the parent dichalcogenides reveals a systematic structure-activity relationship for different compositions of alloys, and it is found that the composition MoS1.0Se1.0 shows the highest HER activity amongst the catalysts studied. The tunable electronic structure of MoS2/MoSe2 upon Se/S incorporation probably assists in the realization of high HER activity.
Toward designing the next generation of resorbable biomaterials for orthopedic applications, we studied poly(ε-caprolactone) (PCL) composites containing graphene. The role, if any, of the functionalization of graphene on mechanical properties, stem cell response, and biofilm formation was systematically evaluated. PCL composites of graphene oxide (GO), reduced GO (RGO), and amine-functionalized GO (AGO) were prepared at different filler contents (1%, 3%, and 5%). Although the addition of the nanoparticles to PCL markedly increased the storage modulus, this increase was largest for GO followed by AGO and RGO. In vitro cell studies revealed that the AGO and GO particles significantly increased human mesenchymal stem cell proliferation. AGO was most effective in augmenting stem cell osteogenesis leading to mineralization. Bacterial studies revealed that interaction with functionalized GO induced bacterial cell death because of membrane damage, which was further accentuated by amine groups in AGO. As a result, AGO composites were best at inhibiting biofilm formation. The synergistic effect of oxygen containing functional groups and amine groups on AGO imparts the optimal combination of improved modulus, favorable stem cell response, and biofilm inhibition in AGO-reinforced composites desired for orthopedic applications. This work elucidates the importance of chemical functionalization of graphene in polymer composites for biomedical applications.
A layered MPS3-type compound, FePS3, is introduced
as an electrocatalyst for hydrogen evolution reaction (HER). The non-noble
metal-based FePS3 is a semiconductor that could be solvent
exfoliated into few-layer, two-dimensional (2D) nanosheets. The 2D
thin sheets exhibit very good catalytic activity and stability toward
HER over a wide pH range of acidic, alkaline, phosphate buffer, and
3.5 wt % aqueous NaCl solutions. The Tafel slope and exchange current
density in acidic medium are determined to be ∼(45–50)
mV dec–1 and 1 ± 0.2 × 10–3 A cm–2, respectively. The stability of
the catalyst is found to be very good. Density functional theory calculations
reveal P and S as favorable hydrogen adsorption sites. This material
opens up a new class of ternary, layered semiconductors for various
electrocatalytic studies and might also become important from a device
physics point of view.
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