Unveiling carcinogenic pollutant levels in environmental water samples through facile fabrication of gold nanoparticles on sulfur-doped graphitic carbon nitride.

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 µA mM-1 cm-2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed.

Direct Adsorption of Graphene Oxide on a Glassy Carbon Electrode: An Investigation of Its Adsorption and Electrochemical Activity.

Different modes of attachment of graphene oxide (GO) on an electrode surface resulted in unusual catalytic behavior respective of attachment because of film thickness. The present work investigates the direct adsorption of GO to the surface of a glassy carbon (GC) electrode. Scanning electron microscopy images revealed that multilayers of GO get adsorbed on the GC substrate and the adsorption was limited by folding up of the GO sheets at their edges. π-π and hydrogen bonding interactions between the GO and GC substrate flagged the adsorption of GO. pH studies revealed that higher adsorption of GO was achieved at pH = 3 rather than at pH = 7 and 10. Even though the electroactive surface area of adsorbed GO (GOads) was not remarkable (0.069 cm2), upon electrochemical reduction of GOads (Er-GOads), the electroactive surface area was escalated to be 0.174 cm2. Similarly, the RCT of Er-GOads was boosted to 2.9 kΩ compared to GOads which is 19 kΩ. Open circuit voltage was recorded to study the adsorption of GO on the GC electrode. Multilayered GO best fitted with the Freundlich adsorption isotherm, and the Freundlich constants like n and KF were found to be 4 and 0.992, respectively. The Freundlich constant "n" revealed the adsorption of GO on the GC substrate to be a physisorption process. Furthermore, the electrocatalytic performance of Er-GOads was demonstrated by taking uric acid as a probe. The modified electrode showed excellent stability toward the determination of uric acid.

Hybridization of Co3S4 and Graphitic Carbon Nitride Nanosheets for High-performance Nonenzymatic Sensing of H2O2.

The development of efficient H2O2 sensors is crucial because of their multiple functions inside and outside the biological system and the adverse effects that a higher concentration can cause. This work reports a highly sensitive and selective non-enzymatic electrochemical H2O2 sensor achieved through the hybridization of Co3S4 and graphitic carbon nitride nanosheets (GCNNS). The Co3S4 is synthesized via a hydrothermal method, and the bulk g-C3N4 (b-GCN) is prepared by the thermal polycondensation of melamine. The as-prepared b-GCN is exfoliated into nanosheets using solvent exfoliation, and the composite with Co3S4 is formed during nanosheet formation. Compared to the performances of pure components, the hybrid structure demonstrates excellent electroreduction towards H2O2. We investigate the H2O2-sensing performance of the composite by cyclic voltammetry, differential pulse voltammetry, and amperometry. As an amperometric sensor, the Co3S4/GCNNS exhibits high sensitivity over a broad linear range from 10 nM to 1.5 mM H2O2 with a high detection limit of 70 nM and fast response of 3 s. The excellent electrocatalytic properties of the composite strengthen its potential application as a sensor to monitor H2O2 in real samples. The remarkable enhancement of the electrocatalytic activity of the composite for H2O2 reduction is attributed to the synergistic effect between Co3S4 and GCNNS.

Systematic Study on Morphological, Electrochemical Impedance, and Electrocatalytic Activity of Graphitic Carbon Nitride Modified on a Glassy Carbon Substrate from Sequential Exfoliation in Water.

Several researchers have synthesized graphitic carbon nitride (GCN) from various precursors and attached it to electrode substrates after exfoliation under different conditions and have reported inconsistent data on electrochemical impedance, electroactive surface areas, and electrocatalytic activity. Thus, the present study aims to study the same systematically in addition to morphology after modifying GCN on the GC substrate from different exfoliation times in water assisted by sonication. The GCN was prepared from urea by bulk condensation pyrolysis and then attached to the GC substrate by drop casting to study its morphology, electrochemical impedance, and electrocatalytic activity with respect to exfoliation. The SEM image of a GCN-modified GC plate after 15 and 30 min of exfoliation shows bulky structure whereas thin sheets of GCN were noticed after 120 min of exfoliation. On the other hand, broken sheets were observed when GCN was coated from beyond 120 min of exfoliation. The electrochemical impedance studies show that the charge transfer resistance (RCT) of GCN modified from 15 and 30 min of exfoliation was higher than that for the bare GC electrode. However, it started to decrease while increasing the exfoliation time, and 1.8 kΩ was obtained after 120 min of exfoliation. The RCT value was again increased to 3.2 and 5.0 kΩ for GCN coated after 150 and 180 min of exfoliation, respectively. The electroactive surface area (EASA) of GCN modified by 15 and 30 min of exfoliation was less than that of the bare GC electrode, whereas it was 3.8-fold higher for GCN coated from 120 min of exfoliation. The electrocatalytic activity of the GC electrodes modified with GCN was then tested by studying ascorbic acid (AA) and dopamine (DA) oxidation and reduction of hydrogen peroxide (HP). Among the different exfoliation times, GCN modified from 120 min of exfoliation displayed the highest electrocatalytic activity toward AA, DA, and HP. This was attributed to its higher EASA and lower charge-transfer resistance.