Insights into the Electrochemical CO2RR Performance and Binding of Small Molecules on Quaternary Thiospinels Ag2FeSn3S8 and Cu2FeSn3S8.

Using a mechanical synthesis method in the form of ball milling and an additional annealing step, a novel and accelerated route for the synthesis of the thiospinels toyohaite (Ag2FeSn3S8) and rhodostannite (Cu2FeSn3S8) was discovered. Both thiospinels display faradaic efficiencies of up to 73% for CO2 reduction to CO using an organic electrolyte in an H-type cell. The materials were furthermore implemented in a zero-gap electrolyzer, with toyohaite producing 22% CO and 52% H2 at 100 mA cm-2 and rhodostannite 28% CO and 37% H2. The catalytically active sites are studied using density functional theory, revealing strong CO binding interactions on both Ag and Cu, whereas Sn is found to contribute to the decomposition of Ag2FeSn3S8 and Cu2FeSn3S8 by coordination with oxygen. Postmortem analysis of the thiospinel-based electrodes by means of SEM-EDX, XRD, XPS, and Mössbauer spectroscopy showed sulfur leaching from the catalysts after applying 100 mA cm-2. These spectroscopic results-in conjunction with DFT calculations of the oxidized surfaces-suggest that the catalytically active species consists of metal oxides. As a conversion of the metal sulfides into the corresponding metallic species was observed via XRD, the decomposition pathways of both catalysts were also computed using DFT; thus, elucidating the energetically most favorable decomposition products and expanding the possible composition of the catalysts postelectrolysis.

Electroplated Electrodes for Continuous and Mass-Efficient Electrochemical Hydrogenation.

Electrocatalytic hydrogenations (ECH) enable the reduction of organic substrates upon usage of electric current and present a sustainable alternative to conventional processes if green electricity is used. Opposed to most current protocols for electrode preparation, this work presents a one-step binder- and additive-free production of silver- and copper-electroplated electrodes. Controlled adjustment of the preparation parameters allows for the tuning of catalyst morphology and its electrochemical properties. Upon optimization of the deposition protocol and carbon support, high faradaic efficiencies of 93 % for the ECH of the Vitamin A- and E-synthon 2-methyl-3-butyn-2-ol (MBY) are achieved that can be maintained at current densities of 240 mA cm-2 and minimal catalyst loadings of 0.2 mg cm-2, corresponding to an unmatched production rate of 1.47 kgMBE gcat -1 h-1. For a continuous hydrogenation process, the protocol can be directly transferred into a single-pass operation mode giving a production rate of 1.38 kgMBE gcat -1 h-1. Subsequently, the substrate spectrum was extended to a total of 17 different C-C-, C-O- and N-O-unsaturated compounds revealing the general applicability of the reported process. Our results lay an important groundwork for the development of electrochemical reactors and electrodes able to directly compete with the palladium-based thermocatalytic state of the art.

Developing electrochemical hydrogenation towards industrial application.

Electrochemical hydrogenation reactions gained significant attention as a sustainable and efficient alternative to conventional thermocatalytic hydrogenations. This tutorial review provides a comprehensive overview of the basic principles, the practical application, and recent advances of electrochemical hydrogenation reactions, with a particular emphasis on the translation of these reactions from lab-scale to industrial applications. Giving an overview on the vast amount of conceivable organic substrates and tested catalysts, we highlight the challenges associated with upscaling electrochemical hydrogenations, such as mass transfer limitations and reactor design. Strategies and techniques for addressing these challenges are discussed, including the development of novel catalysts and the implementation of scalable and innovative cell concepts. We furthermore present an outlook on current challenges, future prospects, and research directions for achieving widespread industrial implementation of electrochemical hydrogenation reactions. This work aims to provide beginners as well as experienced electrochemists with a starting point into the potential future transformation of electrochemical hydrogenations from a laboratory curiosity to a viable technology for sustainable chemical synthesis on an industrial scale.

Opening the pathway towards a scalable electrochemical semi-hydrogenation of alkynols via earth-abundant metal chalcogenides.

Electrosynthetic methods are crucial for a future sustainable transformation of the chemical industry. Being an integral part of many synthetic pathways, the electrification of hydrogenation reactions gained increasing interest in recent years. However, for the large-scale industrial application of electrochemical hydrogenations, low-resistance zero-gap electrolysers operating at high current densities and high substrate concentrations, ideally applying noble-metal-free catalyst systems, are required. Because of their conductivity, stability, and stoichiometric flexibility, transition metal sulfides of the pentlandite group have been thoroughly investigated as promising electrocatalysts for electrochemical applications but were not investigated for electrochemical hydrogenations of organic materials. An initial screening of a series of first row transition metal pentlandites revealed promising activity for the electrochemical hydrogenation of alkynols in water. The most active catalyst within the series was then incorporated into a zero-gap electrolyser enabling the hydrogenation of alkynols at current densities of up to 240 mA cm-2, Faraday efficiencies of up to 75%, and an alkene selectivity of up to 90%. In this scalable setup we demonstrate high stability of catalyst and electrode for at least 100 h. Altogether, we illustrate the successful integration of a sustainable catalyst into a scalable zero-gap electrolyser establishing electrosynthetic methods in an application-oriented manner.

Enhancing the CO2 Electroreduction of Fe/Ni-Pentlandite Catalysts by S/Se Exchange.

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 Fe4.5 Ni4.5 S8 (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 (CO2 RR) than their sulfide counterparts, the authors investigated the influence of stepwise S/Se exchange in seleno-pentlandites Fe4.5 Ni4.5 S8-Y SeY (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 CO2 RR with Fe4.5 Ni4.5 S4 Se4 revealing the highest activity for CO formation. Under galvanostatic conditions in acetonitrile, Fe4.5 Ni4.5 S4 Se4 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.

Sustainable and rapid preparation of nanosized Fe/Ni-pentlandite particles by mechanochemistry.

In recent years, metal-rich sulfides of the pentlandite type (M9S8) have attracted considerable attention for energy storage applications. However, common synthetic routes towards pentlandites either involve energy intensive high temperature procedures or solvothermal methods with specialized precursors and non-sustainable organic solvents. Herein, we demonstrate that ball milling is a simple and efficient method to synthesize nanosized bimetallic pentlandite particles (Fe4.5Ni4.5S8, Pn) with an average size of ca. 250 nm in a single synthetic step from elemental- or sulfidic mixtures. We herein highlight the effects of the milling ball quantity, precursor types and milling time on the product quality. Along this line, Raman spectroscopy as well as temperature/pressure monitoring during the milling processes provide valuable insights into mechanistic differences between the mechanochemical Pn-formation. By employing the obtained Pn-nanosized particles as cathodic electrocatalysts for water splitting in a zero-gap PEM electrolyzer we provide a comprehensive path for a potential sustainable future process involving non-noble metal catalysts.

Seleno-analogues of pentlandites (Fe4.5Ni4.5S8-YSeY, Y = 1-6): tuning bulk Fe/Ni sulphoselenides for hydrogen evolution.

We herein present a series of hitherto unprecedented seleno-pentlandites (Fe4.5Ni4.5S8-YSeY). By analysing the influence of S/Se exchange on the catalyst structure and activity in the electrochemical hydrogen evolution reaction we herein showcase the potential and limitations of homologous S/Se exchanges within pentlandite HER catalysts.