Crystal Phase Transition Creates a Highly Active and Stable RuCX Nanosurface for Hydrogen Evolution Reaction in Alkaline Media.

Although metastable crystal structures have received much attention owing to their utilization in various fields, their phase-transition to a thermodynamic structure has attracted comparably little interest. In the case of nanoscale crystals, such an exothermic phase-transition releases high energy within a confined surface area and reconstructs surface atomic arrangement in a short time. Thus, this high-energy nanosurface may create novel crystal structures when some elements are supplied. In this work, the creation of a ruthenium carbide (RuCX , X < 1) phase on the surface of the Ru nanocrystal is discovered during phase-transition from cubic-close-packed to hexagonal-close-packed structure. When the electrocatalytic hydrogen evolution reaction (HER) is tested in alkaline media, the RuCX exhibits a much lower overpotential and good stability relative to the counterpart Ru-based catalysts and the state-of-the-art Pt/C catalyst. Density functional theory calculations predict that the local heterogeneity of the outermost RuCX surface promotes the bifunctional HER mechanism by providing catalytic sites for both H adsorption and facile water dissociation.

Theoretical and Experimental Understanding of Hydrogen Evolution Reaction Kinetics in Alkaline Electrolytes with Pt-Based Core-Shell Nanocrystals.

The free energy of H adsorption (ΔGH) on a metallic catalyst has been taken as a descriptor to predict the hydrogen evolution reaction (HER) kinetics but has not been well applied in alkaline media. To assess this, we prepare Pd@Pt and PdH@Pt core-shell octahedra enclosed by Pt(111) facets as model catalysts for controlling the ΔGH affected by the ligand, the strain, and their ensemble effects. The Pt shell thickness is adjusted from 1 to 5 atomic layers by varying the amount of Pt precursor added during synthesis. In an alkaline electrolyte, the HER activity of core-shell models is improved either by the construction of core-shell structures or by the increased number of Pt shells. These experimental results are in good agreement with the ΔGH values calculated by the first-principles density functional theory with a complex surface strained core-shell slab model. However, enhanced HER activities of Pd@Pt and PdH@Pt core-shell nanocrystals over the Pt catalyst are inconsistent with the thermodynamic ΔGH scaling relationship only but can be explained by the work function and apparent ΔGH models that predict the interfacial electric field for the HER.

Recent advances in electrocatalysts toward the oxygen reduction reaction: the case of PtNi octahedra.

Designing highly efficient and durable electrocatalysts for the oxygen reduction reaction (ORR), the key step for the operation of polymer electrolyte membrane fuel cells (PEMFCs), is of a pivotal importance for advancing PEMFC technology. Since the most significant progress has been made on Pt3Ni(111) alloy surfaces, nanoscale PtNi alloy octahedra enclosed by (111) facets have emerged as promising electrocatalysts toward the ORR. However, because their practical uses have been hampered by the cost, sluggish reaction kinetics, and poor durability, recent advances have engendered a wide variety of structure-, size-, and composition-controlled bimetallic PtNi octahedra. Herein, we therefore review the important recent developments of PtNi octahedral electrocatalysts point by point to give an overview of the most promising strategies. Specifically, the present review article focuses on the synthetic methods for the PtNi octahedra, the core-shell and multi-metallic strategies for performance improvement, and their structure-, size-, and composition-control-based ORR activity. By considering the results achieved in this field, a prospect for this alloy nanocatalysts system for future sustainable energy applications is also proposed.

Pt and Pt-Ni(OH)2 Electrodes for the Hydrogen Evolution Reaction in Alkaline Electrolytes and Their Nanoscaled Electrocatalysts.

The design and synthesis of Pt-based electrocatalysts for the hydrogen evolution reaction (HER) are of great importance for the successful development of hydrogen-based alternative energy technologies. Although Pt is considered to be the most active catalyst for the HER, its reaction performance is limited in alkaline solutions owing to a slow rate for water dissociation. Therefore, many research groups have intensively investigated reaction mechanisms and developed system designs and efficient Pt-based catalysts to enhance the alkaline HER. Herein, we summarize the catalytic surface specificity of Pt and Pt-Ni(OH)2 materials to control the kinetics of the alkaline HER. In particular, we increase our understanding of Ni(OH)2 -modified Pt surfaces and the corresponding nanoscaled Pt-Ni(OH)2 electrocatalysts to improve the sluggish water-dissociation step, and this knowledge will guide us to future sustainable energy applications of advanced nanomaterials.

Shape-controlled Pt nanocubes directly grown on carbon supports and their electrocatalytic activity toward methanol oxidation.

Synthesis of shape-controlled Pt nanocrystals is substantial and important for enhancing chemical and electrochemical reactions. However, the removal of capping agents, shape-controlling chemicals, on Pt surfaces is essential prior to conducting the catalytic reactions. Here we report a facile one-pot synthesis of Pt nanocubes directly grown on carbon supports (Pt nanocubes/C) with modulating the kinetic reaction factors for shaping the nanocrystals, but without adding any capping agents for preserving the clean Pt surfaces. Well-dispersed Pt nanocubes/C shows enhanced activity and long-term stability toward methanol oxidation reaction compared to the commercial Pt/C catalyst.

Phytoaccumulation of Heavy Metals in Natural Vegetation at the Municipal Wastewater Site in Abbottabad, Pakistan.

Heavy metal accumulation in crops and soils from wastewater irrigation poses a significant threat to the human health. A study was carried out to investigate the removal potential of heavy metals (HM) by native plant species, namely Cannabis sativa L., Chenopodium album L., Datura stramonium L., Sonchus asper L., Amaranthus viridus L., Oenothera rosea (LHer), Xanthium stramonium L., Polygonum macalosa L., Nasturtium officinale L. and Conyza canadensis L. growing at the municipal wastewater site in Abbottabad city, Pakistan. The HM concentrations varied among plants depending on the species. Metal concentrations across species varied in the order iron (Fe) > zinc (Zn) > chromium (Cr) > nickel (Ni) > cadmium (Cd). Majority of the species accumulated more HM in roots than shoots. Among species, the concentrations (both in roots and shoots) were in the order C. sativa > C. album > X. stramonium > C. canadensis > A. viridus > N. officinale > P. macalosa > D. stramonium > S. asper > O. rosea. No species was identified as a hyperaccumulator. All species exhibited a translocation factor (TF) less than 1. Species like C. sativa, C. album and X. stramonium gave higher (> 1) biological concentration factor (BCF) and biological accumulation coefficient (BAC) especially for Fe, Cr and Cd than other species. Higher accumulation of heavy metals in these plant species signifies the general application of these species for phytostabilization and phytoextraction of HM from polluted soils.