Strain Effects on the Oxidation of CO and HCOOH at Au-Pd Core-Shell Nanoparticles

The mechanism of CO and HCOOH electrooxidation in an acidic solution on carbon-supported Au–Pd core–shell nanoparticles was investigated by differential electrochemical mass spectrometry and in situ Fourier transform infrared (FTIR) spectroscopy. Analysis performed in nanostructures with 1.3 ± 0.1 nm (CS1) and 9.9 ± 1.1 nm (CS10) Pd shells provides compelling evidence that the mechanism of adsorbed CO (COads) oxidation is affected by structural and electronic effects introduced by the Au cores. In the case of CS10, a band associated with adsorbed OH species (OHads) is observed in the potential range of CO oxidation. This feature is not detected in the case of CS1, suggesting that the reaction follows an alternative mechanism involving COOHads species. The faradaic charge associated with COads oxidation as well as the Stark slope measured from FTIR indicates that the overall affinity and orbital coupling of CO to Pd are weaker for CS1 shells. FTIR spectroscopy also revealed the presence of HCOOads intermediate species only in the case of CS1. This observation allowed us to conclude that the higher activity of CS10 toward this reaction is due to a fast HCOOads oxidation step, probably involving OHads, to generate CO2. Density functional theory calculations are used to estimate the contributions of the so-called ligand and strain effects on the local density of states of the Pd d-band. The calculations strongly suggest that the key parameter contributing to the change in mechanism is the effective lattice strain

Tuning CO2 electroreduction efficiency at Pd shells on Au nanocores

The faradaic efficiency of CO2 electroreduction is significantly affected by the thickness of Pd nanoshells on Au cores. The ratio of hydrogen evolution to CO2 reduction was determined by differential electrochemical mass spectrometry. Decreasing the Pd shell thickness from 10 to 1 nm leads to a twofold increase in faradaic efficiency

Ongoing harlequin toad declines suggest the amphibian extinction crisis is still an emergency

Biodiversity loss is extreme in amphibians. Despite ongoing conservation action, it is difficult to determine where we stand in overcoming their extinction crisis. Among the most threatened amphibians are the 131 Neotropical harlequin toads. Many of them declined since the 1980s with several considered possibly extinct. Recently, more than 30 species have been rediscovered, raising hope for a reversing trend in the amphibian extinction crisis. We use past and present data available for harlequin toads (Atelopus), to examine whether the amphibian extinction crisis is still in an emergency state. Since 2004 no species has improved its population status, suggesting that recovery efforts have not been successful. Threats include habitat change, pathogen spread and climate change. More mitigation strategies need implementation, especially habitat protection and disease management, combined with captive conservation breeding. With harlequin toads serving as a model, it is clear that the amphibian extinction crisis is still underway. The status of the harlequin toads has not improved since 2004 despite species rediscoveries accompanied by increasing conservation efforts, and habitat destruction and degradation continue to threaten them today, according to an analysis of population status records over the period 2004-2022

Intraperitoneal drain placement and outcomes after elective colorectal surgery: international matched, prospective, cohort study

Many surgeons routinely place intraperitoneal drains after elective colorectal surgery. However, enhanced recovery after surgery guidelines recommend against their routine use owing to a lack of clear clinical benefit. This study aimed to describe international variation in intraperitoneal drain placement and the safety of this practice