Controlling the Size and Pattern Pitch of Ni(OH)2 Nanoclusters Using Dip-Pen Nanolithography to Improve Water Oxidation.

We use dip-pen nanolithography to accurately pattern Ni(OH)2 nanoclusters on a metachemical surface with an exceptionally large surface area. The distance between the nanoclusters can be manipulated to control the oxygen-evolution reaction current and overpotential, thereby improving the efficiency of the water-splitting process while using minute amounts of the catalyst.

Unique activity of a Keggin POM for efficient heterogeneous electrocatalytic OER.

Polyoxometalates (POMs) have been well studied and explored in electro/photochemical water oxidation catalysis for over a decade. The high solubility of POMs in water has limited its use in homogeneous conditions. Over the last decade, different approaches have been used for the heterogenization of POMs to exploit their catalytic properties. This study focused on a Keggin POM, K6[CoW12O40], which was entrapped in a sol-gel matrix for heterogeneous electrochemical water oxidation. Its entrapment in the sol-gel matrix enables it to catalyze the oxygen evolution reaction at acidic pH, pH 2.0. Heterogenization of POMs using the sol-gel method aids in POM's recyclability and structural stability under electrochemical conditions. The prepared sol-gel electrode is robust and stable. It achieved electrochemical water oxidation at a current density of 2 mA/cm2 at a low overpotential of 300 mV with a high turnover frequency (TOF) of 1.76 [mol O2 (mol Co)-1s-1]. A plausible mechanism of the electrocatalytic process is presented.

Oxidation mechanism of porous Zr2Fe used as a hydrogen getter.

We determined the oxidation mechanism of porous ST-198, which mainly comprises Zr2Fe. Oxidation kinetics depended on temperature, oxygen partial pressure, and oxidation extent. The passivation role of oxidation in hydrogen scavenging is probably due to the development of a surface oxide, independent of oxygen concentration. Zr2Fe would be a superior hydrogen getter in oxygen-contaminated environments at high temperatures, as most oxygen will be consumed at the outer shell by mass transfer limitations, protecting the bulk of the getter for hydrogen scavenging.