Cobalt incorporated sulfur-doped graphitic carbon nitride with bismuth oxychloride (Co/S-gC3N4/BiOCl) heterojunction is prepared by an ultrasonically assisted hydrothermal treatment. The heterojunction materials have employed in photoelectrochemical (PEC) water splitting. The PEC activity and stability of the materials are promoted by constructing an interface between the visible light active semiconductor photocatalyst and cocatalysts. The photocurrent density of Co-9% S-gC3N4/BiOCl has attained 393.0 μA cm-2 at 1.23 V vs. RHE, which is 7-fold larger than BiOCl and ~3-fold higher than 9% S-gC3N4/BiOCl. The enhanced PEC activity can be attributed to the improved electron-hole charge separation and the boosted charge transfer is confirmed by photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) analysis. The fabricated Co/S-gC3N4/BiOCl nanohybrid material has exhibited high stability of up to 10,800 s (3 h) at 1.23 V vs. RHE during PEC water splitting reaction and the obtained photo-conversion efficiency is 3.7-fold greater than S-gC3N4/BiOCl and 17-fold higher than BiOCl. The FESEM and HRTEM images have revealed the formation of heterojunction interface between S-gC3N4 and BiOCl and the elemental mapping has confirmed the presence of cobalt over S-gC3N4/BiOCl. The heterojunction interface has facilitated the photo-excited charge separation and transport across the electrode/electrolyte interface and also the flat-band potential, which is confirmed by Mott-Schottky analysis.
A photoelectrochemical (PEC) sensor with excellent sensitivity and detection toward copper (II) ions (Cu2+) was developed using a cadmium sulphide-reduced graphene oxide (CdS-rGO) nanocomposite on an indium tin oxide (ITO) surface, with triethanolamine (TEA) used as the sacrificial electron donor. The CdS nanoparticles were initially synthesized via the aerosol-assisted chemical vapor deposition (AACVD) method using cadmium acetate and thiourea as the precursors to Cd2+ and S2-, respectively. Graphene oxide (GO) was then dip-coated onto the CdS electrode and sintered under an argon gas flow (50 mL/min) for the reduction process. The nanostructured CdS was adhered securely to the ITO by a continuous network of rGO that also acted as an avenue to intensify the transfer of electrons from the conduction band of CdS. The photoelectrochemical results indicated that the ITO/CdS-rGO photoelectrode could facilitate broad UV-visible light absorption, which would lead to a higher and steady-state photocurrent response in the presence of TEA in 0.1 M KCl. The photocurrent decreased with an increase in the concentration of Cu2+ ions. The photoelectrode response for Cu2+ ion detection had a linear range of 0.5-120 μM, with a limit of detection (LoD) of 16 nM. The proposed PEC sensor displayed ultra-sensitivity and good selectivity toward Cu2+ ion detection.
This work demonstrates a high-performance hybrid asymmetric supercapacitor (HASC) workable in very high current density of 30 A g-1 with in-situ pyrolytic processed sulfur-doped graphitic carbon nitride/cobalt disulfide (S-gC3N4/CoS2) materials and bio-derived carbon configuration and achievement of high electrochemical stability of 89% over 100,000 cycles with the coulombic efficiency of 99.6%. In the electrochemical studies, the S-gC3N4/CoS2-II electrode showed a high specific capacity of 180 C g-1 at 1 A g-1 current density in the half-cell configuration. The HASC cell was fabricated using S-gC3N4/CoS2-II material and orange peel derived activated carbon as a positive and negative electrode with a maximum operating cell potential of 1.6 V, respectively. The fabricated HASC delivered a high energy density of 26.7 Wh kg-1 and power density of 19.8 kW kg-1 in aqueous electrolyte. The prominent properties in specific capacity and cycling stability could be attributed to the CoS2 nanoparticles engulfed into the S-gC3N4 framework which provides short transport distance of the ions, strong interfacial interaction, and improving structural stability of the S-gC3N4/CoS2-II materials.
In this study, a disposable and simple electrochemical immunosensor was fabricated for the detection of carcinoembryonic antigen. In this method, silver nanoparticles (AgNPs) were mixed with reduced graphene oxide (rGO) to modify the surface of screen-printed carbon electrode (SPE). Initially, AgNPs-rGO modified-SPEs were fabricated by using simple electrochemical deposition method. Then the carcinoembryonic antigen (CEA) was immobilized between the primary antibody and horseradish peroxidase (HRP)-conjugated secondary antibody onto AgNPs-rGO modified-SPEs to fabricate a sandwich-type electrochemical immunosensor. The proposed method could detect the CEA with a linear range of 0.05-0.50µgmL-1 and a detection limit down to 0.035µgmL-1 as compared to its non-sandwich counterpart, which yielded a linear range of 0.05-0.40µgmL-1, with a detection limit of 0.042µgmL-1. The immunosensor showed good performance in the detection of carcinoembryonic antigen, exhibiting a simple, rapid and low-cost. The immunosensor showed a higher sensitivity than an enzymeless sensor.
A newly developed CdS/rGO/CC electrode was prepared based on a flexible carbon cloth (CC) substrate with cadmium sulfide (CdS) nanoparticles and reduced graphene oxide (rGO). The CdS was synthesized using an aerosol-assisted chemical vapor deposition (AACVD) method, and the graphene oxide was thermally reduced on the modified electrode surface. The existence of rGO in the CdS-modified electrode increased the photocurrent intensity of the CdS/rGO/CC-modified electrode by three orders of magnitude, compared to that of the CdS/ITO electrode and two orders of magnitude higher than the CdS/CC electrode. A new visible-light-prompt photoelectrochemical sensor was developed based on the competitive binding reaction of Cu(2+) and CdS on the electrode surface. The results showed that the effect of the Cu(2+) on the photocurrent response was concentration-dependent over the linear ranges of 0.1-1.0 μM and 1.0-40.0 μM with a detection limit of 0.05 μM. The results of a selectivity test showed that this modified electrode has a high response toward Cu(2+) compared to other heavy metal ions. The proposed CdS/rGO/CC electrode provided a significantly high potential current compared to other reported values, and could be a practical tool for the fast, sensitive, and selective determination of Cu(2+).
Immunosensors based on gold nanoparticles and reduced graphene oxide (AuNPs/rGO)-modified screen-printed electrodes (SPEs) were successfully synthesized using an electrochemical deposition method. The modified SPEs were characterized using a field emission scanning electron microscope (FESEM) and Raman spectroscopy to analyze the morphology and composition of AuNPs and rGO. Both the FESEM and Raman spectroscopy revealed that the AuNPs were successfully anchored on the thin film of rGO deposited on the surface of the SPEs. Characterization with a ferri-ferrocyanide couple [Fe(CN)6(3-/4-)] showed that the electron transfer kinetic between the analyte and electrode was enhanced after the modification with the AuNPs/rGO composite on the electrode surface, in addition to increasing the effective surface area of the electrode. The modified SPE was immobilized with a sandwich type immunosensor to mimic the ELISA (enzyme-linked immunosorbent assay) immunoassay. The modified SPE that was fortified with the sandwich type immunosensor exhibited double electrochemical responses in the detection of carcinoembryonic antigen (CEA), with linear ranges of 0.5-50 ng/mL and 250-2000 ng/mL and limits of detection of 0.28 ng/mL and 181.5 ng/mL, respectively.
A silver nanoparticle-decorated N,S-co-doped TiO2 nanocomposite was successfully prepared and used as an efficient photoanode in high-performance dye-sensitized solar cells (DSSCs) with N719 dye. The DSSCs assembled with the N,S-TiO2@Ag-modified photoanode demonstrated an enhanced solar-to-electrical energy conversion efficiency of 8.22%, which was better than that of a DSSC photoanode composed of unmodified TiO2 (2.57%) under full sunlight illumination (100 mWcm(-2), AM 1.5 G). This enhanced efficiency was mainly attributed to the reduced band gap energy, improved interfacial charge transfer, and retarded charge recombination process. The influence of the Ag content on the overall efficiency was also investigated, and the optimum Ag content with N,S-TiO2 was found to be 20 wt%. Because of the enhanced solar energy conversion efficiency of the N,S-TiO2@Ag nanocomposite, it should be considered as a potential photoanode for high-performance DSSCs.
The energy density of conventional supercapacitors is in the range of 6-10 Wh kg-1, which has restricted them from many applications that require devices with long durations. Herein, we report a method for enhancing the energy density of a device through the parallel stacking of five copper foils coated on each side with graphene nanoplatelets. Microporous papers immersed in 2 M aqueous sodium sulphate were used as separators. With a low contact resistance of 0.05 Ω, the supercapacitor yielded an optimum specific energy density and a specific power density of 24.64 Wh kg-1 and 402 W kg-1 at 0.8 V, respectively. The working potential was increased to 2.4 V when three of the supercapacitors were connected in series, forming a tandem device. Its potential for real applications was manifested by the ability to light up a light-emitting diode for 40 s after charging for 60 s.
Titanium dioxide (TiO2) with highly exposed {001} facets was synthesized through a facile solvo-thermal method and its surface was decorated by using reduced graphene oxide (rGO) sheets. The morphology and chemical composition of the prepared rGO/TiO2 {001} nanocomposite were examined by using suitable characterization techniques. The rGO/TiO2 {001} nanocomposite was used to modify glassy carbon electrode (GCE), which showed higher electrocatalytic activity towards the oxidation of dopamine (DA) and ascorbic acid (AA), when compared to unmodified GCE. The differential pulse voltammetric studies revealed good sensitivity and selectivity nature of the rGO/TiO2 {001} nanocomposite modified GCE for the detection of DA in the presence of AA. The modified GCE exhibited a low electrochemical detection limit of 6 μM over the linear range of 2-60 μM. Overall, this work provides a simple platform for the development of GCE modified with rGO/TiO2 {001} nanocomposite with highly exposed {001} facets for potential electrochemical sensing applications.
Gold nanorods (Au NRs) are elongated nanoparticles with unique optical properties which depend on their shape anisometry. The Au NR-based longitudinal localized surface plasmon resonance (longitudinal LSPR) band is very sensitive to the surrounding local environment and upon the addition of target analytes, the interaction between the analytes and the surface of the Au NRs leads to a change in the longitudinal LSPR band. This makes it possible to devise Au NR probes with application potential to the detection of toxic metal ions with an improved limit of detection, response time, and selectivity for the fabrication of sensing devices. The effective surface modification of Au NRs helps in improving their selectivity and sensitivity toward the detection of toxic metal ions. In this review, we discuss different methods for the preparation of surface modified Au NRs for the detection of toxic metal ions based on the LSPR band of the Au NRs and the types of interactions between the surface of Au NRs and metal ions. We summarize the work that has been done on Au NR-based longitudinal LSPR detection of environmentally toxic metal ions, sensing mechanisms, and the current progress in various modified Au NR-based longitudinal LSPR sensors for toxic metal ions. Finally, we discuss the applications of Au NR-based longitudinal LSPR sensors to real sample analysis and some of the future challenges facing longitudinal LSPR-based sensors for the detection of toxic metal ions toward commercial devices.
This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I₃(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.
The fabrication of an electrochemical sensor based on an iron oxide/graphene modified glassy carbon electrode (Fe3O4/rGO/GCE) and its simultaneous detection of dopamine (DA) and ascorbic acid (AA) is described here. The Fe3O4/rGO nanocomposite was synthesized via a simple, one step in-situ wet chemical method and characterized by different techniques. The presence of Fe3O4 nanoparticles on the surface of rGO sheets was confirmed by FESEM and TEM images. The electrochemical behavior of Fe3O4/rGO/GCE towards electrocatalytic oxidation of DA was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) analysis. The electrochemical studies revealed that the Fe3O4/rGO/GCE dramatically increased the current response against the DA, due to the synergistic effect emerged between Fe3O4 and rGO. This implies that Fe3O4/rGO/GCE could exhibit excellent electrocatalytic activity and remarkable electron transfer kinetics towards the oxidation of DA. Moreover, the modified sensor electrode portrayed sensitivity and selectivity for simultaneous determination of AA and DA. The observed DPVs response linearly depends on AA and DA concentration in the range of 1-9 mM and 0.5-100 µM, with correlation coefficients of 0.995 and 0.996, respectively. The detection limit of (S/N = 3) was found to be 0.42 and 0.12 µM for AA and DA, respectively.
In this report, silver nanoparticles (Ag NPs) were successfully deposited on graphene oxide (GO) sheets to form GO-Ag nanocomposite using garlic extract and sunlight and the nanocomposite modified glassy carbon (GC) electrode was applied as an electrochemical sensor for the detection of nitrite ions. The formation of GO-Ag nanocomposite was confirmed by using UV-visible absorption spectroscopy, TEM, XRD and FTIR spectroscopy analyses. Further, TEM pictures showed a uniform distribution Ag on GO sheets with an average size of 19 nm. The nanocomposite modified electrode produced synergistic catalytic current in nitrite oxidation with a negative shift in overpotential. The limit of detection (LOD) values were found as 2.1 µM and 37 nM, respectively using linear sweep voltammetry (LSV) and amperometric i-t curve techniques. The proposed sensor was stable, reproducible, sensitive and selective toward the detection nitrite and could be applied for the detection of nitrite in real water sample.
Nitrogen-doped graphene quantum dots (N-GQDs) were decorated on a three-dimensional (3D) MoS2-reduced graphene oxide (rGO) framework via a facile hydrothermal method. The distribution of N-GQDs on the 3D MoS2-rGO framework was confirmed using X-ray photoelectron spectroscopy, energy dispersive X-ray elemental mapping, and high-resolution transmission electron microscopy techniques. The resultant 3D nanohybrid was successfully demonstrated as an efficient electrocatalyst toward the oxygen reduction reaction (ORR) under alkaline conditions. The chemical interaction between the electroactive N-GQDs and MoS2-rGO and the increased surface area and pore size of the N-GQDs/MoS2-rGO nanohybrid synergistically improved the ORR onset potential to +0.81 V vs reversible hydrogen electrode (RHE). Moreover, the N-GQDs/MoS2-rGO nanohybrid showed better ORR stability for up to 3000 cycles with negligible deviation in the half-wave potential (E 1/2). Most importantly, the N-GQDs/MoS2-rGO nanohybrid exhibited a superior methanol tolerance ability even under a high concentration of methanol (3.0 M) in alkaline medium. Hence, the development of a low-cost metal-free graphene quantum dot-based 3D nanohybrid with high methanol tolerance may open up a novel strategy to design selective cathode electrocatalysts for direct methanol fuel cell applications.
In this work, lipase from Candida rugosa was immobilized onto chitosan/graphene oxide beads. This was to provide an enzyme-immobilizing carrier with excellent enzyme immobilization activity for an enzyme group requiring hydrophilicity on the immobilizing carrier. In addition, this work involved a process for the preparation of an enzymatically active product insoluble in a reaction medium consisting of lauric acid and oleyl alcohol as reactants and hexane as a solvent. This product enabled the stability of the enzyme under the working conditions and allowed the enzyme to be readily isolated from the support. In particular, this meant that an enzymatic reaction could be stopped by the simple mechanical separation of the "insoluble" enzyme from the reaction medium. Chitosan was incorporated with graphene oxide because the latter was able to enhance the physical strength of the chitosan beads by its superior mechanical integrity and low thermal conductivity. The X-ray diffraction pattern showed that the graphene oxide was successfully embedded within the structure of the chitosan. Further, the lipase incorporation on the beads was confirmed by a thermo-gravimetric analysis. The lipase immobilization on the beads involved the functionalization with coupling agents, N-hydroxysulfosuccinimide sodium (NHS) and 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC), and it possessed a high enzyme activity of 64 U. The overall esterification conversion of the prepared product was 78% at 60 °C, and it attained conversions of 98% and 88% with commercially available lipozyme and novozyme, respectively, under similar experimental conditions.
In the present investigation, gold-silver@titania (Au-Ag@TiO2) plasmonic nanocomposite materials with different Au and Ag compositions were prepared using a simple one-step chemical reduction method and used as photoanodes in high-efficiency dye-sensitized solar cells (DSSCs). The Au-Ag incorporated TiO2 photoanode demonstrated an enhanced solar-to-electrical energy conversion efficiency of 7.33%, which is ∼230% higher than the unmodified TiO2 photoanode (2.22%) under full sunlight illumination (100 mW cm-2, AM 1.5G). This superior solar energy conversion efficiency was mainly due to the synergistic effect between the Au and Ag, and their surface plasmon resonance effect, which improved the optical absorption and interfacial charge transfer by minimizing the charge recombination process. The influence of the Au-Ag composition on the overall energy conversion efficiency was also explored, and the optimized composition with TiO2 was found to be Au75-Ag25. This was reflected in the femtosecond transient absorption dynamics in which the electron-phonon interaction in the Au nanoparticles was measured to be 6.14 ps in TiO2/Au75:Ag25, compared to 2.38 ps for free Au and 4.02 ps for TiO2/Au100:Ag0. The slower dynamics indicates a more efficient electron-hole separation in TiO2/Au75:Ag25 that is attributed to the formation of a Schottky barrier at the interface between TiO2 and the noble metal(s) that acts as an electron sink. The significant boost in the solar energy conversion efficiency with the Au-Ag@TiO2 plasmonic nanocomposite showed its potential as a photoanode for high-efficiency DSSCs.