The generation of hydrogen from water using sunlight could potentially form the basis of a clean and renewable source of energy. Various water-splitting methods have been investigated previously, but the use of photocatalysts to split water into stoichiometric amounts of H2 and O2 (overall water splitting) without the use of external bias or sacrificial reagents is of particular interest because of its simplicity and potential low cost of operation. However, despite progress in the past decade, semiconductor water-splitting photocatalysts (such as (Ga1-xZnx)(N1-xOx)) do not exhibit good activity beyond 440 nm (refs 1,2,9) and water-splitting devices that can harvest visible light typically have a low solar-to-hydrogen efficiency of around 0.1%. Here we show that cobalt(II) oxide (CoO) nanoparticles can carry out overall water splitting with a solar-to-hydrogen efficiency of around 5%. The photocatalysts were synthesized from non-active CoO micropowders using two distinct methods (femtosecond laser ablation and mechanical ball milling), and the CoO nanoparticles that result can decompose pure water under visible-light irradiation without any co-catalysts or sacrificial reagents. Using electrochemical impedance spectroscopy, we show that the high photocatalytic activity of the nanoparticles arises from a significant shift in the position of the band edge of the material.

Lidar observations collected during the Lidar In-space Technology Experiment experiment in conjunction with the Meteosat and European Centre for Medium-Range Weather Forecasts data have been used not only to validate the Saharan dust plume conceptual model constructed from the GARP (Global Atmospheric Research Programme) Atlantic Tropical Experiment data, but also to examine the vicissitudes of the Saharan aerosol including their optical depths across the west Africa and east Atlantic regions. Optical depths were evaluated from both the Meteosat and lidar data. Back trajectory calculations were also made along selected lidar orbits to verify the characteristic anticyclonic rotation of the dust plume over the eastern Atlantic as well as to trace the origin of a dust outbreak over West Africa. A detailed synoptic analysis including the satellite-derived optical depths, vertical lidar backscattering cross section profiles, and back trajectories of the 16-19 September 1994 Saharan dust outbreak over the eastern Atlantic and its origin over West Africa during the 12-15 September period have been presented. In addition, lidar-derived backscattering profiles and optical depths were objectively analyzed to investigate the general features of the dust plume and its geographical variations in optical thickness. These analyses validated many of the familiar characteristic features of the Saharan dust plume conceptual model such as (i) the lifting of the aerosol over central Sahara and its subsequent transport to the top of the Saharan air layer (SAL), (ii) the westward rise of the dust layer above the gradually deepening marine mixed layer and the sinking of the dust-layer top, (iii) the anticyclonic gyration of the dust pulse between two consecutive trough axes, (iv) the dome-shaped structure of the dust-layer top and bottom, (v) occurrence of a middlelevel jet near the southern boundary of the SAL, (vi) transverse-vertical circulations across the SAL front including their possible role in the initiation of a squall line to the southside of the jet that ultimately developed into a tropical storm, and (vii) existence of satellite-based high optical depths to the north of the middle-level jet in the ridge region of the wave. Furthermore, the combined analyses reveal a complex structure of the dust plume including its origin over North Africa and its subsequent westward migration over the Atlantic Ocean. The dust plume over the west African coastline appears to be composed of two separate but narrow plumes originating over the central Sahara and Lake Chad regions, in contrast to one single large plume shown in the conceptual model. Lidar observations clearly show that the Saharan aerosol over North Africa not only consist of background dust (Harmattan haze) but also wind-blown aerosol from fresh dust outbreaks. They further exhibit maximum dust concentration near the middle-level jet axis with downward extension of heavy dust into the marine boundary layer including a clean dust-free trade wind inversion to the north of the d...

Microscopic understanding of interaction between H2O and MAPbI3 (CH3NH3PbI3) is essential to further improve efficiency and stability of perovskite solar cells. A complete picture of perovskite from initial physical uptake of water molecules to final chemical transition to its monohydrate MAPbI3·H2O is obtained with in situ infrared spectroscopy, mass monitoring, and X-ray diffraction. Despite strong affinity of MA to water, MAPbI3 absorbs almost no water from ambient air. Water molecules penetrate the perovskite lattice and share the space with MA up to one H2O per MA at high-humidity levels. However, the interaction between MA and H2O through hydrogen bonding is not established until the phase transition to monohydrate where H2O and MA are locked to each other. This lack of interaction in water-infiltrated perovskite is a result of dynamic orientational disorder imposed by tetragonal lattice symmetry. The apparent inertness of H2O along with high stability of perovskite in an ambient environment provides a solid foundation for its long-term application in solar cells and optoelectronic devices.

Although Raman spectral fingerprints of Co 3 O 4 have been well established, the infrared spectrum of Co 3 O 4 is less understood due to its dependence on sample morphologies and experimental configurations. The same is true for both Raman and infrared spectra of CoO. In this study, we present a comprehensive optical characterization of Co 3 O 4 and CoO with Raman scattering and Fourier transform infrared spectroscopy (FTIR). Two of the transverse optical (TO) phonons and their corresponding longitudinal optical (LO) phonons of Co 3 O 4 above 500 cm −1 are observed in both transmission and diffuse reflectance with LO/TO intensity ratios depending on particle size and the incident angle of FTIR beam. CoO is featured by a broad infrared band around 510 cm −1 . In contrast to many previous reports, no Raman-active phonon line is observed, which is in agreement with the selection rule for rock-salt CoO. Nevertheless, CoO can still be characterized by Raman scattering from magnetic excitations in its antiferromagnetic phase at low temperature and a two-phonon Raman band at ∼1060 cm −1 .

TiO(2) photocatalytic oxidation (PCO) of As(III) in the normal air-saturated aqueous solutions has been widely studied. Yet no consensus has been achieved on the mechanism whether superoxide is the main oxidant, although many approaches have been taken. (Photo)electrochemical method can minimize changes to TiO(2) surface and could therefore not alter the normal mechanism. In this Article, both this approach and As(III) oxidation kinetic measurements were performed to clarify the disputed mechanism. Under a sufficient cathodic bias potential, the dark oxidation of As(III) by superoxide could occur, but both the reaction rate and the columbic efficiency were rather low, suggesting that it is a weak oxidant. However, under UV light, both the reaction rate and the columbic efficiency were greatly enhanced even at potentials negative enough to eliminate photohole participation, indicating that more efficient oxidants than superoxide were produced. Under UV illumination and enough positive potential where superoxide was absent, the As(III) oxidation was the most highly efficient. The columbic efficiency of photoholes was much higher than that of superoxide. In the normal aerated aqueous solutions and at open circuit, although the total contribution of superoxide and its derivates to the PCO of As(III) was considerably high (up to 43%), it was not more than that of photohole (57%). In addition, the reported various approaches taken to elucidate the mechanism were discussed, and the resulting disputes can be clarified by these findings. It was demonstrated that (photo)electrochemical method could provide direct and undisputed evidence to reveal the truth mechanics issues.