Modeling practical performance limits of photoelectrochemical water splitting based on the current state of materials research.

Photoelectrochemical (PEC) water splitting is a means to store solar energy in the form of hydrogen. Knowledge of practical limits for this process can help researchers assess their technology and guide future directions. We develop a model to quantify loss mechanisms in PEC water splitting based on the current state of materials research and calculate maximum solar-to-hydrogen (STH) conversion efficiencies along with associated optimal absorber band gaps. Various absorber configurations are modeled considering the major loss mechanisms in PEC devices. Quantitative sensitivity analyses for each loss mechanism and each absorber configuration show a profound impact of both on the resulting STH efficiencies, which can reach upwards of 25 % for the highest performance materials in a dual stacked configuration. Higher efficiencies could be reached as improved materials are developed. The results of the modeling also identify and quantify approaches that can improve system performance when working with imperfect materials.

Branched TiO2 nanorods for photoelectrochemical hydrogen production.

We report a hierarchically branched TiO(2) nanorod structure that serves as a model architecture for efficient photoelectrochemical devices as it simultaneously offers a large contact area with the electrolyte, excellent light-trapping characteristics, and a highly conductive pathway for charge carrier collection. Under Xenon lamp illumination (UV spectrum matched to AM 1.5G, 88 mW/cm(2) total power density), the branched TiO(2) nanorod array produces a photocurrent density of 0.83 mA/cm(2) at 0.8 V versus reversible hydrogen electrode (RHE). The incident photon-to-current conversion efficiency reaches 67% at 380 nm with an applied bias of 0.6 V versus RHE, nearly two times higher than the bare nanorods without branches. The branches improve efficiency by means of (i) improved charge separation and transport within the branches due to their small diameters, and (ii) a 4-fold increase in surface area which facilitates the hole transfer at the TiO(2)/electrolyte interface.

UC Pd: a new form of Pd/C for Sonogashira couplings.

Screening of different sources of Pd/C shows reagents of highly variable nanoparticle sizes and oxidation states of the metal. Typically, catalysts with higher surface area are viewed as likely to be the more reactive. In this paper a new form of Pd/C, "UC Pd" is described that is shown to contain larger nanoparticles yet it is the most reactive catalyst of those sold commercially for Sonogashira coupling reactions. UC Pd functions efficiently in the absence of a copper co-catalyst, under very mild and "green" conditions using inexpensive 95% EtOH at 50 degrees C. It is also the only form of Pd/C that can be recycled. In side-by-side reactions with several commercially available forms of Pd/C, none compete successfully with UC Pd under standardized conditions. Physical data obtained from extensive surface analysis using TEM, XRD, XPS, and CO-TPD measurements lead to an explanation behind the unique reactivity of this new recyclable form of Pd/C.