Ambiguities and best practices in the determination of active sites and real surface area of monometallic electrocatalytic interfaces.

Determining the number of electrocatalytically accessible sites (ECAS) and real surface area (RSA) for any given electrocatalyst precisely is important in energy conversion electrocatalysis as these are directly used in the determination of intrinsic activity markers. For monometallic electrocatalysts and electrocatalysts of just one type of active site, there believed to be ways of making precise determination of ECAS and RSA using underpotential deposition (UPD), stripping, and redox-charge integration employing transient voltammetric sweeping techniques. This transient nature of sweeping techniques makes the determination of ECAS and RSA relatively less reliable. This study is directed at examining the effects of scan rate in the determination of ECAS and RSA taking Ni(OH)2/CC and Pt wire as model catalytic electrodes. The results suggest that the scan rate and the determined ECAS and RSA values are inversely related and the lowest possible scan rate set experiment was witnessed to give the highest possible ECAS or RSA values with LSV/CV.

High and reversible oxygen uptake in carbon dot solutions generated from polyethylene facilitating reactant-enhanced solar light harvesting.

Solar-driven photocatalysis is emerging as a key chemical transformation strategy due to its favourable energy economy. However, in photocatalytic oxidation reactions where molecular oxygen (O2) is a reactant, achieving higher efficiency requires an O2-saturated environment in order to maintain a high oxygen level on the catalyst surface, necessitating an additional energy-consuming step of O2 separation from air. Here we show that in the presence of carbon quantum dots (CQDs), the oxygen content and the ability of O2 to diffuse in water increase significantly. We first demonstrate a novel strategy to convert several grams of polyethylene, a stubborn pollutant, into highly photoactive CQDs by stepwise dehydrogenation and graphitization. In a typical CQD concentration of ∼1 mg ml-1, the oxygen level in water reaches ∼640 µM, double that of pure water inferring an extremely high O2 content of ∼1 wt% associated with CQDs under ambient conditions. Therefore, when the CQDs were used to catalyze photo-oxidation of aromatic alcohols by sunlight, the efficiency was found higher than previous instances despite those employing high oxygen pressure, temperature and expensive materials. Besides waste polyethylene utilization, the uniqueness of oxygen enrichment in CQD solutions may offer immense prospects including those in photo-oxidation reactions.

Emerging Materials in Heterogeneous Electrocatalysis Involving Oxygen for Energy Harvesting.

Water-based renewable energy cycle involved in water splitting, fuel cells, and metal-air batteries has been gaining increasing attention for sustainable generation and storage of energy. The major challenges in these technologies arise due to the poor kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reactions (OER), besides the high cost of the catalysts. Attempts to address these issues have led to the development of many novel and inexpensive catalysts as well as newer mechanistic insights, particularly so in the last three-four years when more catalysts have been investigated than ever before. With the growing emphasis on bifunctionality, that is, materials that can facilitate both reduction and evolution of oxygen, this review is intended to discuss all major families of ORR, OER, and bifunctional catalysts such as metals, alloys, oxides, other chalcogenides, pnictides, and metal-free materials developed during this period in a single platform, while also directing the readers to specific and detailed review articles dealing with each family. In addition, each section highlights the latest theoretical and experimental insights that may further improve ORR/OER performances. The bifunctional catalysts being sufficiently new, no consensus appears to have emerged about the efficiencies. Therefore, a statistical analysis of their performances by considering nearly all literature reports that have appeared in this period is presented. The current challenges in rational design of these catalysts as well as probable strategies to improve their performances are presented.

Self-Assembled Molecular Hybrids of CoS-DNA for Enhanced Water Oxidation with Low Cobalt Content.

Water oxidation in alkaline medium was efficiently catalyzed by the self-assembled molecular hybrids of CoS-DNA that had 20 times lower Co loading than the commonly used loading. The morphological outcome was directed by varying the molar ratio of metal precursor Co(Ac)2 and DNA and three different sets of CoS-DNA molecular hybrids, viz. CoS-DNA(0.036), CoS-DNA(0.06), and CoS-DNA(0.084) were prepared. These morphologically distinct hybrids had shown similar electrocatalytic behavior, because of the fact that they all contained the same cobalt content. The CoS-DNA(0.036), CoS-DNA(0.06), and CoS-DNA(0.084) required very low overpotentials of 350, 364, and 373 mV at a current density of 10 mA cm-2 (1 M KOH), respectively. The advantages of lower overpotential, lower Tafel slope (42.7 mV dec-1), high Faradaic efficiency (90.28%), high stability and reproducibility after all, with a lower cobalt loading, have certainly shown the worth of these molecular hybrids in large-scale water oxidation. Moreover, since DNA itself a good binder, CoS-DNA molecular hybrids were directly casted on substrate electrodes and used after drying. It also showed minimum intrinsic resistance as DNA is a good ionic and electronic conductor. Besides, the present method may also be extended for the preparation of other active electrocatalysts for water splitting.