Bismuth vanadate (BiVO4) is a promising photoelectrode material for the oxidation of water, but fundamental studies of this material are lacking. To address this, we report electrical and photoelectrochemical (PEC) properties of BiVO4 single crystals (undoped, 0.6% Mo, and 0.3% W:BiVO4) grown using the floating zone technique. We demonstrate that a small polaron hopping conduction mechanism dominates from 250 to 400 K, undergoing a transition to a variable-range hopping mechanism at lower temperatures. An anisotropy ratio of ~3 was observed along the c axis, attributed to the layered structure of BiVO4. Measurements of the ac field Hall effect yielded an electron mobility of ~0.2 cm(2) V(-1) s(-1) for Mo and W:BiVO4 at 300 K. By application of the Gärtner model, a hole diffusion length of ~100 nm was estimated. As a result of low carrier mobility, attempts to measure the dc Hall effect were unsuccessful. Analyses of the Raman spectra showed that Mo and W substituted for V and acted as donor impurities. Mott-Schottky analysis of electrodes with the (001) face exposed yielded a flat band potential of 0.03-0.08 V versus the reversible H2 electrode, while incident photon conversion efficiency tests showed that the dark coloration of the doped single crystals did not result in additional photocurrent. Comparison of these intrinsic properties to those of other metal oxides for PEC applications gives valuable insight into this material as a photoanode.

We report a synergistic effect involving hydrogenation and nitridation cotreatment of TiO(2) nanowire (NW) arrays that improves the water photo-oxidation performance under visible light illumination. The visible light (>420 nm) photocurrent of the cotreated TiO(2) is 0.16 mA/cm(2) and accounts for 41% of the total photocurrent under simulated AM 1.5 G illumination. Electron paramagnetic resonance (EPR) spectroscopy reveals that the concentration of Ti(3+) species in the bulk of the TiO(2) following hydrogenation and nitridation cotreatment is significantly higher than that of the sample treated solely with ammonia. It is believed that the interaction between the N-dopant and Ti(3+) is the key to the extension of the active spectrum and the superior visible light water photo-oxidation activity of the hydrogenation and nitridation cotreated TiO(2) NW arrays.

Although Li-ion batteries have emerged as the battery of choice for electric vehicles and large-scale smart grids, significant research efforts are devoted to identifying materials that offer higher energy density, longer cycle life, lower cost, and/or improved safety compared to those of conventional Li-ion batteries based on intercalation electrodes. By moving beyond intercalation chemistry, gravimetric capacities that are 2–5 times higher than that of conventional intercalation materials (e.g., LiCoO2 and graphite) can be achieved. The transition to higher-capacity electrode materials in commercial applications is complicated by several factors. This Review highlights the developments of electrode materials and characterization tools for rechargeable lithium-ion batteries, with a focus on the structural and electrochemical degradation mechanisms that plague these systems.

Reaching the goal of economical photoelectrochemical (PEC) water splitting will likely require the combination of efficient solar absorbers with high activity electrocatalysts for the hydrogen and oxygen evolution reactions (HER and OER). Toward this goal, we synthesized an amorphous FeOOH (a-FeOOH) phase that has not previously been studied as an OER catalyst. The a-FeOOH films show activity comparable to that of another OER cocatalyst, Co-borate (Co-Bi), in 1 M Na2CO3, reaching 10 mA/cm(2) at an overpotential of ∼550 mV for 10 nm thick films. Additionally, the a-FeOOH thin films absorb less than 3% of the solar photons (AM1.5G) with energy greater than 1.9 eV, are homogeneous over large areas, and act as a protective layer separating the solution from the solar absorber. The utility of a-FeOOH in a realistic system is tested by depositing on amorphous Si triple junction solar cells with a photovoltaic efficiency of 6.8%. The resulting a-FeOOH/a-Si devices achieve a total water splitting efficiency of 4.3% at 0 V vs RHE in a three-electrode configuration and show no decrease in efficiency over the course of 4 h.

Metal chalcogenides, pnictides, and carbides, labeled collectively as metal X-ides, have become an exciting new class of water oxidation electrocatalysts, but there is a lack of agreement regarding the composition of the "true" catalyst. The most prominent theories are that the X-ides are either completely oxidized, left unoxidized, or transformed into core@shell particles upon testing. Here, we examine examples of each conjecture, summarizing the conflicting viewpoints on catalyst identity and offering guidelines for more rigorous identification in the future. Most studies indicate that at least partial oxidation of the catalyst surface is critical to high performance, likely caused by an increased catalyst surface area upon oxidation or improved charge transfer in the X-ide cores. Therefore, more thorough and uniform long-term testing and nanoscale chemical analysis are essential to determine how these factors relate to catalyst performance.