Yun Hau Ng

Z-Schematic Water Splitting into H2 and O2 Using Metal Sulfide as a Hydrogen-Evolving Photocatalyst and Reduced Graphene Oxide as a Solid-State Electron Mediator

Z-schematic water splitting was successfully demonstrated using metal sulfide photocatalysts that were usually unsuitable for water splitting as single particulate photocatalysts due to photocorrosion. When metal sulfide photocatalysts with a p-type semiconductor character as a H2-evolving photocatalyst were combined with reduced graphene oxide-TiO2 composite as an O2-evolving photocatalyst, water splitting into H2 and O2 in a stoichiometric amount proceeded. In this system, photogenerated electrons in the TiO2 with an n-type semiconductor character transferred to the metal sulfide through a reduced graphene oxide to achieve water splitting. Moreover, this system was active for solar water splitting.

Water Splitting and CO2 Reduction under Visible Light Irradiation Using Z-Scheme Systems Consisting of Metal Sulfides, CoOx-Loaded BiVO4, and a Reduced Graphene Oxide Electron Mediator

Metal sulfides are highly active photocatalysts for water reduction to form H2 under visible light irradiation, whereas they are unfavorable for water oxidation to form O2 because of severe self-photooxidation (i.e., photocorrosion). Construction of a Z-scheme system is a useful strategy to split water into H2 and O2 using such photocorrosive metal sulfides because the photogenerated holes in metal sulfides are efficiently transported away. Here, we demonstrate powdered Z-schematic water splitting under visible light and simulated sunlight irradiation by combining metal sulfides as an H2-evolving photocatalyst, reduced graphene oxide (RGO) as an electron mediator, and a visible-light-driven BiVO4 as an O2-evolving photocatalyst. This Z-schematic photocatalyst composite is also active in CO2 reduction using water as the sole electron donor under visible light.

Efficient Water Splitting Catalyzed by Cobalt Phosphide-Based Nanoneedle Arrays Supported on Carbon Cloth.

Efficient and low-cost electrocatalysts for water splitting are essential for solar fuel production. Herein, we report that nanoarrays of CoP supported on carbon cloth are an efficient bifunctional catalyst for overall water splitting. The catalyst exhibits remarkable activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media, delivering a current density of 10 mA cm(-2) at an overpotential of 281 mV for OER and 95 mV for HER. During electrocatalysis, the surface of the CoP catalyst was covered with a layer of CoOx , which was the active species. However, the CoP core and the nanoarray morphology contributed significantly to the activity.

Transforming Anodized WO3 Films into Visible-Light-Active Bi2WO6 Photoelectrodes by Hydrothermal Treatment

We directly transformed anodized tungsten oxide film (WO3·2H2O) into bismuth tungstate (Bi2WO6) by substituting the intercalated water molecules with [Bi2O2](2+) in a hydrothermal treatment. The resultant Bi2WO6 was readily used as an electrode to produce anodic photocurrent in H2 evolution on the Pt counter electrode observed under visible light irradiation.

Wrapping the walls of n-TiO2 nanotubes with p-CuInS2 nanoparticles using pulsed-electrodeposition for improved heterojunction photoelectrodes

The CuInS(2) (CIS) nanoparticles were wrapped uniformly throughout the inner and outer walls of TNTs (TNT) by using square wave pulsed-electrodeposition. This structure enables the CuInS(2)-TiO(2) (CIS-TNT) to exhibit p-n junction diode behavior and enhanced photoelectrochemical properties.

BiVO4 {010} and {110} Relative Exposure Extent: Governing Factor of Surface Charge Population and Photocatalytic Activity

The {010} and {110} crystal facets of monoclinic bismuth vanadate (m-BiVO4) has been demonstrated to be the active reduction and oxidation sites, respectively. Here, we show using dual-faceted m-BiVO4 with distinctly different dominant exposed facets, one which is {010}-dominant and the other {110}-dominant, contrary to prediction, the former m-BiVO4 exhibits superior photooxidation activities. The population of photogenerated electrons and holes on the surface are revealed to be proportional to the respective surface areas of {010} and {110} exposed on m-BiVO4, as evidenced by steady-state photoluminescence (PL) measurements in the presence of charge scavengers. The better photoactivity of {010}-dominant m-BiVO4 is attributed to prompt electron transfer facilitated by the presence of more photogenerated electrons on the larger {010} surface. Additionally, the greater extent of electron trapping in {110}-dominant m-BiVO4 also deteriorates its photoactivity by inducing electron-hole pair recombination.

An electrochemical sensing platform based on a reduced graphene oxide–cobalt oxide nanocube@platinum nanocomposite for nitric oxide detection

We report a facile one-pot hydrothermal synthesis of a reduced graphene oxide–cobalt oxide nanocube@platinum (rGO–Co3O4@Pt) nanocomposite and its application toward the electrochemical detection of nitric oxide (NO). The rGO–Co3O4@Pt nanocomposite was characterized by field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) mapping, X-ray diffraction (XRD) and Raman analyses. The nanocomposite modified glassy carbon (GC) electrode was used for the electrochemical oxidation of nitric oxide (NO) and it showed better catalytic performance in terms of catalytic peak current and shift in overpotential when compared to those of rGO, Co3O4 nanocubes and rGO–Co3O4 nanocomposite modified electrodes. The rGO–Co3O4@Pt nanocomposite modified electrode showed a better sensing ability toward the in situ generated NO in NO2− containing phosphate buffer solution (PBS) than the other controlled modified electrodes. The Pt nanoparticles present in the nanocomposite could enhance the sensing performance and the limit of detection (LOD) was found to be 1.73 μM with a signal-to-noise (S/N) ratio of ∼3 using the amperometric i–t curve technique. Furthermore, the nanocomposite modified electrode showed selectivity toward the detection of NO in the presence of a 100-fold higher concentration of other physiologically important analytes. The proposed sensor was stable, reproducible and selective toward the detection of NO.

Alternative strategies in improving the photocatalytic and photoelectrochemical activities of visible light-driven BiVO4: a review

The research interest on bismuth vanadate (BiVO4) has heightened over the past decade due to its proven high activity for water oxidation and organic degradations under visible light. Although metal doping and water-oxidation cocatalyst loading have been widely demonstrated to be useful to overcome the poor electron transport and slow water oxidation kinetics of BiVO4, the efficiency of this material is still greatly limited by poor charge separation. Various efforts directed at modifying the surface and bulk properties to improve the performance of BiVO4-based materials have therefore been developed, including crystal facet engineering, coupling with graphitic carbon material, annealing treatment, and nanoscaling. This review aims to provide insights into the most recent progress in these strategies in regard to their influences on the charge separation, transport, and transfer aspects of BiVO4, all of which are crucial to govern photochemical conversion efficiency. Understanding of these charge kinetics in relation to the properties of BiVO4 is of fundamental importance for rational design of BiVO4 with optimum structures, which may serve as a general guideline for the fabrication of metal oxide photocatalysts.

Sodium Fluoride-Assisted Modulation of Anodized TiO2 Nanotube for Dye-Sensitized Solar Cells Application

This work reports the use of sodium fluoride (in ethylene glycol electrolyte) as the replacement of hydrofluoric acid and ammonium fluoride to fabricate long and perpendicularly well-aligned TiO₂ nanotube (TNT) (up to 21 μm) using anodization. Anodizing duration, applied voltage and electrolyte composition influenced the geometry and surface morphologies of TNT. The growth mechanism of TNT is interpreted by analyzing the current transient profile and the total charge density generated during anodization. The system with low water content (2 wt %) yielded a membrane-like mesoporous TiO₂ film, whereas high anodizing voltage (70 V) resulted in the unstable film of TNT arrays. An optimized condition using 5 wt % water content and 60 V of anodizing voltage gave a stable array of nanotube with controllable length and pore diameter. Upon photoexcitation, TNTs synthesized under this condition exhibited a slower charge recombination rate as nanotube length increased. When made into cis-diisothiocyanato-bis(2,2̀-bipyridyl-4,4̀-dicarboxylato) ruthenium(II) bis (tetrabutyl-ammonium)(N719) dye-sensitized solar cells, good device efficiency at 3.33 % based on the optimized TNT arrays was achieved with longer electron time compared with most mesoporous TiO₂ films.

Electrospun Polyacrylonitrile–Ionic Liquid Nanofibers for Superior PM2.5 Capture Capacity

Ambient fine particulate matter (PM) affects both human health and climate. To reduce the PM2.5 (mass of particles below 2.5 μm in diameter) concentration of an individuals living environment, ionic liquid-modified polyacrylonitrile (PAN) nanofibers with superior PM2.5 capture capacity were prepared by electrospinning. Ionic liquid diethylammonium dihydrogen phosphate (DEAP) with high viscosity and hydrophilicity was involved during the electrospinning process. Observations by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and water contact angle measurement suggested that the modification of DEAP on PAN effectively altered the morphology (roughness) and surface properties (hydrophilicity) of the PAN nanofibers. The PM2.5 capture measurement was performed in a closed and static system, which mimicked the static hazy weather without wind flow. As a result, DEAP-modified PAN nanofibers exhibited significantly enhanced PM2.5 capture capacity compared to that of the bare PAN nanofibers. This can be attributed to the improved surface roughness (i.e., improved adsorption sites), hydrophilicity, and dipole moment of PAN upon DEAP modification.