Synthesis and Electrochemical Study of Three-Dimensional Graphene-Based Nanomaterials for Energy Applications.

Graphene is an attractive soft material for various applications due to its unique and exclusive properties. The processing and preservation of 2D graphene at large scales is challenging due to its inherent propensity for layer restacking. Three-dimensional graphene-based nanomaterials (3D-GNMs) preserve their structures while improving processability along with providing enhanced characteristics, which exhibit some notable advantages over 2D graphene. This feature article presents recent trends in the fabrication and characterization of 3D-GNMs toward the study of their morphologies, structures, functional groups, and chemical compositions using scanning electron microscopy, X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Owing to the attractive properties of 3D-GNMs, which include high surface areas, porous structures, improved electrical conductivity, high mechanical strength, and robust structures, they have generated tremendous interest for various applications such as energy storage, sensors, and energy conversion. This article summarizes the most recent advances in electrochemical applications of 3D-GNMs, pertaining to energy storage, where they can serve as supercapacitor electrode materials and energy conversion as oxygen reduction reaction catalysts, along with an outlook.

Synthesis and Electrochemical Study of Mesoporous Nickel-Cobalt Oxides for Efficient Oxygen Reduction.

Development of a cost-effective and efficient electrocatalyst for the sluggish oxygen reduction reaction (ORR) is a crucial challenge for clean energy technologies. In this study, we have synthesized various Ni and Co oxide (NCO) nanomaterials via a facile coprecipitation, followed by the calcination method. The morphology of the formed NCO nanomaterials was controlled by varying the percentage of the Ni and Co precursors, leading to the formation of a template-free mesoporous spinel phase structure of Ni xCo3- xO4. It was found that the number of the octahedral site cations and the defect sites with lower oxygen in the spinel oxides can be tunable by taking appropriate ratios of the Ni and Co precursors. The optimized NCO nanomaterial exhibits superior electrocatalytic activity compared to the mono-metal oxides of NiO and Co3O4 with over 3 times higher current density and ∼0.250 V lower onset potential toward ORR in a 0.1 M KOH solution. Scanning electrochemical microscopy was utilized in mapping the activity of the catalyst and monitoring the ORR products, further confirming that a four-electron transfer pathway was facilitated by the NCO nanomaterial. Moreover, the developed mesoporous NCO nanomaterial exhibits a high methanol tolerance capability and long-term stability when compared to the commercial state-of-the-art Pt/C electrocatalyst. The improvement of the catalytic activity and stability of this advanced NCO nanomaterial toward ORR may be attributed to the facile accessible mesoporous structure, and the abundance of octahedral site cations and defective oxygen sites.

Sensitive Electrochemical Detection of Caffeic Acid in Wine Based on Fluorine-Doped Graphene Oxide.

We report here a novel electrochemical sensor developed using fluorine-doped graphene oxide (F-GO) for the detection of caffeic acid (CA). The synthesized graphene oxide (GO) and F-GO nanomaterials were systematically characterized with a scanning electron microscope (SEM), and the presence of semi-ionic bonds was confirmed in the F-GO using X-ray photoelectron spectroscopy. The electrochemical behaviours of bare glassy carbon electrode (GCE), F-GO/GCE, and GO/GCE toward the oxidation of CA were studied using cyclic voltammetry (CV), and the results obtained from the CV investigation revealed that F-GO/GCE exhibited the highest electrochemically active surface area and electrocatalytic activity in contrast to the other electrodes. Differential pulse voltammetry (DPV) was employed for the analytical quantitation of CA, and the F-GO/GCE produced a stable oxidation signal over the selected CA concentration range (0.5 to 100.0 µM) with a low limit of detection of 0.018 µM. Furthermore, the acquired results from the selectivity studies revealed a strong anti-interference capability of the F-GO/GCE in the presence of other hydroxycinnamic acids and ascorbic acid. Moreover, the F-GO/GCE offered a good sensitivity, long-term stability, and an excellent reproducibility. The practical application of the electrochemical F-GO sensor was verified using various brands of commercially available wine. The developed electrochemical sensor successfully displayed its ability to directly detect CA in wine samples without pretreatment, making it a promising candidate for food and beverage quality control.

Shape-controlled synthesis of Co3O4 for enhanced electrocatalysis of the oxygen evolution reaction.

A facile two-step synthesis of 1D nanorod, 2D nanosheet, and 3D nanocube-shaped Co3O4 was demonstrated. The formed 1D, 2D, and 3D Co3O4 were systematically probed using a structure sensitive electrochemical oxygen evolution reaction (OER), revealing that the 2D nanosheets exhibited higher catalytic activities in contrast to the 1D and 3D Co3O4, due to their high electrochemically active surface area and rich oxygen deficiencies. This study also showed that there was a tradeoff between the 2D and 3D Co3O4 in terms of OER activity and stability.

From graphite to interconnected reduced graphene oxide: one-pot synthesis and supercapacitor application.

An innovative one-pot approach for the scalable production of novel interconnected reduced graphene oxide (IC-RGO) is demonstrated, and we name it the streamlined Hummers method (SHM). The formed IC-RGO represents a new type of three-dimensional platform, promising for many graphene related energy, environmental and medical applications.