Search

The electrochemical reduction of CO2 is an attractive strategy towards the mitigation of environmental pollution and production of bulk chemicals as well as fuels by renewables. The bimetallic sulfide Fe4.5Ni4.5S8 (pentlandite) was recently reported as a cheap and robust catalyst for electrochemical water splitting, as well as for CO2 reduction with a solvent‐dependent product selectivity. Inspired by numerous reports on monometallic sulfoselenides and selenides revealing higher catalytic activity for the CO2 reduction reaction (CO2RR) than their sulfide counterparts, the authors investigated the influence of stepwise S/Se exchange in seleno‐pentlandites Fe4.5Ni4.5S8‐YSeY (Y=1–5) and their ability to act as CO2 reducing catalysts. It is demonstrated that the incorporation of higher equivalents of selenium favors the CO2RR with Fe4.5Ni4.5S4Se4 revealing the highest activity for CO formation. Under galvanostatic conditions in acetonitrile, Fe4.5Ni4.5S4Se4 generates CO with a Faradaic Efficiency close to 100 % at applied current densities of −50 mA cm−2 and −100 mA cm−2. This work offers insight into the tunability of the pentlandite based electrocatalysts for the CO2 reduction reaction. [ABSTRACT FROM AUTHOR]

Metal‐rich chalcogenides composed of highly abundant elements recently emerged as promising catalysts for the electrocatalytic hydrogen evolution reaction (HER). Many of these materials benefit from a high intrinsic conductivity as compared to their chalcogen‐rich congeners, greatly reducing the necessity for conductive additives or sophisticated nanostructuring. Herein, we showcase the high potential of metal‐rich transition‐metal chalcogenides for the electrocatalytic hydrogen formation by summarizing the recent progress achieved with M9S8 (pentlandite type) and M3S2 (heazlewoodite type) based materials, which represent the most frequently applied compositions for this purpose. By a detailed electrochemical comparison of bulk as well as pellet electrodes of metal‐rich Fe4.5Ni4.5S8, we also aim at raising awareness in the community for the inherent differences in catalytic properties of the materials themselves and those of the fabricated electrodes, a point that is often disregarded in reports on HER‐catalyst systems. [ABSTRACT FROM AUTHOR]

Abstract: In order to design more powerful electrocatalysts, developing our understanding of the role of the surface structure and composition of widely abundant bulk materials is crucial. This is particularly true in the search for alternative hydrogen evolution reaction (HER) catalysts to replace platinum. We report scanning electrochemical cell microscopy (SECCM) measurements of the (111)‐crystal planes of Fe4.5Ni4.5S8, a highly active HER catalyst. In combination with structural characterization methods, we show that this technique can reveal differences in activity arising from even the slightest compositional changes. By probing electrochemical properties at the nanoscale, in conjunction with complementary structural information, novel design principles are revealed for application to rational material synthesis. [ABSTRACT FROM AUTHOR]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)