Manash R. Das

In this study, graphene oxide (GO) nanosheets have been used for the adsorption of methyl green, a cationic dye from aqueous solution. GO nanosheets consist of single layered graphite structure decorated with a number of oxygen containing functionalities such as carboxyl, epoxy, ketone, and hydroxyl groups which impart a negative charge density to it in aqueous solution at a wide range of pH. Thus, GO nanosheets can be predicted as a good adsorbent material for the adsorption of cationic species. The adsorption of the methyl green onto the GO nanosheets has been carried out at different experimental conditions such as adsorption kinetics, concentration of adsorbate, pH, and temperature. The kinetics of the adsorption data were analyzed using four kinetic models such as the pseudofirst-order model, pseudosecond-order model, intraparticle diffusion, and the Boyd model to understand the adsorption behavior of methyl green onto the GO nanosheets and the mechanism of adsorption. The kinetics of adsorption result shows that the adsorption maximum was reached at 60 min and follows the linear form of pseudosecond-order kinetics. The adsorption isotherm of adsorption of the methyl green onto the GO nanosheets has been investigated in the pH range of 4 to 9 at 25 °C. The equilibrium data were fitted well to the Langmuir model. Various thermodynamic parameters such as the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) change were also evaluated. The negative value of ΔG indicates spontaneity of the adsorption process of the methyl green–GO system. The interaction of methyl green onto the GO nanosheets has been investigated by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy.

Over the past decade, nanosized metal oxides, metals, and bimetallic particles have been actively researched as enzyme mimetic nanomaterials. However, the common issues with individual nanoparticles (NPs) are stabilization, reproducibility, and blocking of active sites by surfactants. These problems promote further studies of composite materials, where NPs are spread on supports, such as graphene derivatives or dichalcogenide nanosheets. Another promising type of support for NPs is the few-layered hexagonal boron nitride (hBN). In this study, we develop surfactant-free nanocomposites containing Pt NPs dispersed on chemically modified hydrophilic hBN nanosheets (hBNNSs). Ascorbic acid was used as a reducing agent for the chemical reduction of the Pt salt in the presence of hBNNS aqueous colloid, resulting in Pt/hBNNS nanocomposites, which were thoroughly characterized with X-ray diffraction, transmission electron microscopy, dynamic light scattering, and X-ray photoelectron and infrared spectroscopies. Similar to graphene oxide binding the metal NPs more efficiently than pure graphene, hydrophilic hBNNSs well stabilize Pt NPs, with particle size down to around 8 nm. We further demonstrate for the first time that Pt/hBNNS nanocomposites exhibit peroxidase-like catalytic activity, accelerating the oxidation of the classical colorless peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) to its corresponding blue-colored oxidized product in the presence of H2O2. Kinetic and mechanism studies involving terephthalic acid and isopropanol as a fluorescent probe and an •OH radical scavenger, respectively, proved that Pt/hBNNSs assist H2O2 decomposition to active oxygen species (•OH), which are responsible for TMB oxidation. The Pt/hBNNS nanocomposite-assisted oxidation of TMB provides an effective platform for the colorimetric detection of dopamine, an important biomolecule. The presence of increased amounts of dopamine gradually inhibits the catalytic activity of Pt/hBNNSs for the oxidation of TMB by H2O2, thus enabling selective sensing of dopamine down to 0.76 μM, even in the presence of common interfering molecules and on real blood serum samples. The present investigation on Pt/hBNNSs contributes to the knowledge of hBN-based nanocomposites and discovers their new usage as nanomaterials with good enzyme-mimicking activity and dopamine-sensing properties.