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.

Photocatalytic Hydrogen Evolution from Artificial Seawater Splitting over Amorphous Carbon Nitride: Optimization and Process Parameters Study via Response Surface Modeling.

Photocatalytic water splitting has garnered tremendous attention for its capability to produce clean and renewable H2 fuel from inexhaustible solar energy. Until now, most research has focused on scarce pure water as the source of H2, which is not consistent with the concept of sustainable energy. Hence, the importance of photocatalytic splitting of abundant seawater in alleviating the issue of pure water shortages. However, seawater contains a wide variety of ionic components which have unknown effects on photocatalytic H2 production. This work investigates photocatalytic seawater splitting conditions using environmentally friendly amorphous carbon nitride (ACN) as the photocatalyst. The individual effects of catalyst loading (X1), sacrificial reagent concentration (X2), salinity (X3), and their interactive effects were studied via the Box-Behnken design in response surface modeling towards the H2 evolution reaction (HER) from photocatalytic artificial seawater splitting. A second-order polynomial regression model is predicted from experimental data where the variance analysis of the regressions shows that the linear term (X1, X2), the two-way interaction term X1X2, and all the quadratic terms (X12, X22, X23) pose significant effects towards the response of the HER rate. Numerical optimization suggests that the highest HER rate is 7.16 µmol/h, achievable by dosing 2.55 g/L of ACN in 45.06 g sea salt/L aqueous solution containing 17.46 vol% of triethanolamine. Based on the outcome of our findings, an apparent effect of salt ions on the adsorption behavior of the photocatalyst in seawater splitting with a sacrificial reagent has been postulated.

Electrostatic Contribution to the Photo-Assisted Piezoresponse Force Microscopy by Photo-Induced Surface Charge.

The surging interest in manipulating the polarization of piezo/ferroelectric materials by means of light has driven an increasing number of studies toward their light-polarization interaction. One way to investigate such interaction is by performing piezoresponse force microscopy (PFM) while/after the sample is exposed to light illumination. However, caution must be exercised when analyzing and interpreting the data, as demonstrated in this paper, because sizeable photo-response observed in the PFM amplitude image of the sample is shown to be caused by the electrostatic interaction between the photo-induced surface charge and tip. Through photo-assisted Kelvin probe force microscopy (KPFM), positive surface potential is found to be developed near the sample's surface under 405 nm light illumination, whose effects on the measured PFM signal is revealed by the comparative studies on its amplitude curves that are obtained using PFM spectroscopy mode with/without illumination. This work exemplifies the need for complementary use of KPFM, PFM imaging mode, and PFM spectroscopy mode in order to distinguish real behavior from artifacts.

Fractal grid-induced turbulence strength characterization via piezoelectric thin-film flapping velocimetry.

The centerline streamwise and cross-sectional (x/Dh = 0.425) turbulence characteristics of a 2D planar space-filling square-fractal-grid (SFG) composed of self-similar patterns superimposed at multiple length-scales is experimentally unveiled via piezoelectric thin-film flapping velocimetry (PTFV). The fluid-structure-interaction between a flexible piezoelectric thin-film and SFG-generated turbulent flow at ReDh = 4.1 × 104 is investigated by analysis of the thin-film's mechanical response. Measurements of the thin-film-tip deflection δ and induced voltage V demonstrate increasing flow fluctuation strength in the turbulence generation region, followed by rapid decay further downstream of the SFG. Interestingly, SFG-induced turbulence enables the generation of maximum centerline thin-film's response (Vrms, δrms) and millinewton turbulence-forcing (turbulence-induced excitation force acting on the thin-film) Frms which are respectively, 7× and 2× larger than the classical square-regular-grid of similar blockage ratio. The low frequency, large-scale energy-containing eddies at SFG's central opening plays a critical role in driving the thin-film vibration. Most importantly, the SFG-generated turbulence at (y/T = 0.106, z/T = 0.125) away from the centerline allows equivalent mechanical characteristics of turbulence generation and decay, with peak of 1.9× nearer from grid. In short, PTFV provides a unique expression of the SFG-generated turbulence, of which, the equivalent turbulence length-scale and induced-forcing deduced could aid in deciphering the flow dynamics for effective turbulence management.

Energy Band Gap Modulation in Nd-Doped BiFeO3/SrRuO3 Heteroepitaxy for Visible Light Photoelectrochemical Activity.

The ability of band offsets at multiferroic/metal and multiferroic/electrolyte interfaces in controlling charge transfer and thus altering the photoactivity performance has sparked significant attention in solar energy conversion applications. Here, we demonstrate that the band offsets of the two interfaces play the key role in determining charge transport direction in a downward self-polarized BFO film. Electrons tend to move to BFO/electrolyte interface for water reduction. Our experimental and first-principle calculations reveal that the presence of neodymium (Nd) dopants in BFO enhances the photoelectrochemical performance by reduction of the local electron-hole pair recombination sites and modulation of the band gap to improve the visible light absorption. This opens a promising route to the heterostructure design by modulating the band gap to promote efficient charge transfer.

Tunable Spectrum Selectivity for Multiphoton Absorption with Enhanced Visible Light Trapping in ZnO Nanorods.

Observation of visible light trapping in zinc oxide (ZnO) nanorods (NRs) correlated to the optical and photoelectrochemical properties is reported. In this study, ZnO NR diameter and c-axis length respond primarily at two different regions, UV and visible light, respectively. ZnO NR diameter exhibits UV absorption where large ZnO NR diameter area increases light absorption ability leading to high efficient electron-hole pair separation. On the other hand, ZnO NR c-axis length has a dominant effect in visible light resulting from a multiphoton absorption mechanism due to light reflection and trapping behavior in the free space between adjacent ZnO NRs. Furthermore, oxygen vacancies and defects in ZnO NRs are associated with the broad visible emission band of different energy levels also highlighting the possibility of the multiphoton absorption mechanism. It is demonstrated that the minimum average of ZnO NR c-axis length must satisfy the linear regression model of Z p,min = 6.31d to initiate the multiphoton absorption mechanism under visible light. This work indicates the broadening of absorption spectrum from UV to visible light region by incorporating a controllable diameter and c-axis length on vertically aligned ZnO NRs, which is important in optimizing the design and functionality of electronic devices based on light absorption mechanism.

Heteroatom Nitrogen- and Boron-Doping as a Facile Strategy to Improve Photocatalytic Activity of Standalone Reduced Graphene Oxide in Hydrogen Evolution.

Owing to its superior properties and versatility, graphene has been proliferating the energy research scene in the past decade. In this contribution, nitrogen (N-) and boron (B-) doped reduced graphene oxide (rGO) variants were investigated as a sole photocatalyst for the green production of H2 and their properties with respect to photocatalysis were elucidated for the first time. N- and B-rGOs were facilely prepared via the pyrolysis of graphene oxide with urea and boron anhydride as their respective dopant source. The pyrolysis temperature was varied (600-800 °C for N-rGO and 800-1000 °C for B-rGO) in order to modify dopant loading percentage (%) which was found to be influential to photocatalytic activity. N-rGO600 (8.26 N at%) and B-rGO1000 (3.59 B at%), which holds the highest at% from each of their party, exhibited the highest H2 activity. Additionally, the effects of the nature of N and B bonding configuration in H2 photoactivity were also examined. This study demonstrates the importance of dopant atoms in graphene, rendering doping as an effective strategy to bolster photocatalytic activity for standalone graphene derivative photocatalysts.

Tunable photoelectrochemical performance of Au/BiFeO3 heterostructure.

Ferroelectric photoelectrodes, other than conventional semiconductors, are alternative photo-absorbers in the process of water splitting. However, the capture of photons and efficient transfer of photo-excited carriers remain as two critical issues in ferroelectric photoelectrodes. In this work, we overcome the aforementioned issues by decorating the ferroelectric BiFeO3 (BFO) surface with Au nanocrystals, and thus improving the photoelectrochemical (PEC) performance of BFO film. We demonstrate that the internal field induced by the spontaneous polarization of BFO can (1) tune the efficiency of the photo-excited carriers' separation and charge transfer characteristics in bare BFO photoelectrodes, and (2) modulate an extra optical absorption within the visible light region, created by the surface plasmon resonance excitation of Au nanocrystals to capture more photons in the Au/BFO heterostructure. This study provides key insights for understanding the tunable features of PEC performance, composed of the heterostructure of noble metals and ferroelectric materials.

Tuning electronic transport in a self-assembled nanocomposite.

Self-assembled nanocomposites with a high interface-to-volume ratio offer an opportunity to overcome limitations in current technology, where intriguing transport behaviors can be tailored by the choice of proper interactions of constituents. Here we integrated metallic perovskite oxide SrRuO3-wurzite semiconductor ZnO nanocomposites to investigate the room-temperature metal-insulator transition and its effect on photoresponse. We demonstrate that the band structure at the interface can be tuned by controlling the interface-to-volume ratio of the nanocomposites. Photoinduced carrier injection driven by visible light was detected across the nanocomposites. This work shows the charge interaction of the vertically integrated multiheterostructures by incorporating a controllable interface-to-volume ratio, which is essential for optimization of the design and functionality of electronic devices.