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Anion-tuning in metallic chalcogenides has been shown to have a significant impact on their electrocatalytic ability for overall water splitting. In this article, copper-based chalcogenides (Cu₂X, X= O, S, Se, and Te) have been systematically studied to examine the effect of decreasing anion electronegativity and increasing covalency on the electrocatalytic performance. Among the copper chalcogenides, Cu₂Te has the highest oxygen evolution reaction (OER) activity and can sustain high current density of 10 and 50 mA cm⁻²for 12 h. The difference in intrinsic catalytic activity of these chalcogenide surfaces have been also probed through density functional theory calculations, which was used to estimate energy of the catalyst activation step. It was observed that the hydroxyl adsorption on the surface catalytic site is critically important for the onset and progress of OER activity. Consequently, it was also observed that the –OH adsorption energy can be used as a simple but accurate descriptor to explain the catalytic efficiency through volcano-like correlation plot. Such observation will have a significant impact on developing design principle for optimal catalytic surface exhibiting high performance as well as prolonged stability.

 

Recent emphasis on carbon dioxide utilization has necessitated the exploration of different catalyst compositions other than copper-based systems that can significantly improve the activity and selectivity towards specific CO₂ reduction products at low applied potential. In this study, a binary CoTe has been reported as an efficient electrocatalyst for CO₂reduction in aqueous medium under ambient conditions at neutral pH. CoTe showed high Faradaic efficiency and selectivity of 86.83 and 75%, respectively, for acetic acid at very low potential of − 0.25 V vs RHE. More intriguingly, C1 products like formic acid was formed preferentially at slightly higher applied potential achieving high formation rate of 547.24 μmol cm⁻² h⁻¹ at − 1.1 V vs RHE. CoTe showed better CO2RR activity when compared with Co₃O₄, which can be attributed to the enhanced electrochemical activity of the catalytically active transition metal center as well as improved intermediate adsorption on the catalyst surface. While reduced anion electronegativity and improved lattice covalency in tellurides enhance the electrochemical activity of Co, high d-electron density improves the intermediate CO adsorption on the catalyst site leading to CO₂reduction at lower applied potential and high selectivity for C₂products. CoTe also shows stable CO2RR catalytic activity for 50 h and low Tafel slope (50.3 mV dec^–1) indicating faster reaction kinetics and robust functionality. Selective formation of value-added C₂products with low energy expense can make these catalysts potentially viable for integration with other CO₂capture technologies thereby, helping to close the carbon loop.

 

Transition metal selenides have attracted intensive interest as cost-effective electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) because of the continuous thrust in sustainable energy conversion. In this article a Mn-based bifunctional electrocatalyst, MnSe, has been identified which shows efficient OER and ORR activity in alkaline medium. The catalytic activity could be further enhanced by using multiwalled carbon nanotubes (MWCNTs) which increases the charge transfer and electronic conductivity of the catalyst composite. This MnSe@MWCNT catalyst composite exhibits a very low overpotential of 290 mV at 10 mA cm −2 , which outperforms state-of-the-art RuO 2 as well as other oxide based electrocatalysts. Furthermore, the composite's facile OER kinetics was evidenced by its small Tafel slope of 54.76 mV dec −1 and low charge transfer resistance, indicating quick transport of the reactant species at the electrode interface. The MnSe@MWCNT also exhibited efficient electrocatalytic activity for ORR with an E onset of 0.94 V, which is among the best reported to date for chalcogenide based ORR electrocatalysts. More importantly, this MnSe-based ORR electrocatalyst exhibits high degree of methanol tolerance, showing no degradation of catalyst performance in the presence of copious quantities of methanol, thereby out-performing the state-of-the-art Pt electrocatalyst. The catalyst composite also exhibited exceptional functional and compositional stability for OER and ORR after a prolonged period of continuous operation in alkaline medium. The surface Raman analysis after OER revealed the retention of manganese selenide surface with evidence of oxo coordination, confirming the formation of an (oxy)selenide as the active surface for OER. Such efficient bifunctional OER and ORR activity makes this MnSe based catalyst attractive for overall electrolysis in regenerative as well as direct methanol fuel cells. 

CuSe nanostructures exhibit high-efficiency for glucose detection with high sensitivity (19.419 mA mM −1 cm −2 ) and selectivity at a low applied potential of +0.15 V vs. Ag|AgCl, a low detection limit of 0.196 μM and a linear range of glucose detection from 100 nM to 40 μM.