From Meteorite to Life's Building Blocks: A possible Electrochemical Pathway to Amino Acids and Peptide Bonds.

This study explores the electrochemical properties of the carbonaceous Allende CV3 meteorite, focusing on its potential as a Fe-based catalyst derived from Mackinawite iron sulfide for electrocatalytic reactions facilitating nitrogen (N2) fixation into ammonia. Through comprehensive analysis, we not only monitored the evolution of key compounds such as CN-, sulfur/H2S, H2 and carbonyl compounds, but also identified potential reagent carriers, indicating significant implications for the Strecker synthesis of amino acids in space environments. Initial examination revealed the presence of polypeptides, notably sequences including trimer Gly3, pentamer Gly3-Ala2, and hexamer Gly4-(HO-Gly)2. These discoveries greatly enhance our understanding of astrobiological chemistry, offering valuable insights into prebiotic processes and the potential presence of life-building blocks throughout the universe.

A Bifunctional Electrocatalyst for OER and ORR based on a Cobalt(II) Triazole Pyridine Bis-[Cobalt(III) Corrole] Complex.

As alternative energy sources are essential to reach a climate-neutral economy, hydrogen peroxide (H2 O2 ) as futuristic energy carrier gains enormous awareness. However, seeking for stable and electrochemically selective H2 O2 ORR electrocatalyst is yet a challenge, making the design of-ideally-bifunctional catalysts extremely important and outmost of interest. In this study, we explore the application of a trimetallic cobalt(II) triazole pyridine bis-[cobalt(III) corrole] complex CoII TP[CoIII C]2 3 in OER and ORR catalysis due to its remarkable physicochemical properties, fast charge transfer kinetics, electrochemical reversibility, and durability. With nearly 100 % selective catalytic activity towards the two-electron transfer generated H2 O2 , an ORR onset potential of 0.8 V vs RHE and a cycling stability of 50 000 cycles are detected. Similarly, promising results are obtained when applied in OER catalysis. A relatively low overpotential at 10 mA cm-2 of 412 mV, Faraday efficiency 98 % for oxygen, an outstanding Tafel slope of 64 mV dec-1 combined with superior stability.

Elucidating the Origins of High Preferential Crystal Orientation in Quasi-2D Perovskite Solar Cells.

Incorporating large organic cations to form 2D and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. However, due to their low electron mobility, aligning the organic sheets to ensure unimpeded charge transport is critical to rival the high performances of pure 3D systems. While additives such as methylammonium chloride (MACl) can enable this preferential orientation, so far, no complete description exists explaining how they influence the nucleation process to grow highly aligned crystals. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3-fluorobenzylammonium in quasi-2D perovskite solar cells. Upon assisting the crystallization with MACl, films with a degree of preferential orientation of 94%, capable of withstanding moisture levels of 97% relative humidity for 10 h without significant changes in the crystal structure are achieved. Finally, by combining macroscopic, microscopic, and spectroscopic studies, the nucleation process leading to highly oriented perovskite films is elucidated. Understanding this mechanism will aid in the rational design of future additives to achieve more defect tolerant and stable perovskite optoelectronics.

A Bifunctional Electrocatalyst for OER and ORR based on a Cobalt(II) Triazole Pyridine Bis-[Cobalt(III) Corrole] Complex.

As alternative energy sources are essential to reach a climate-neutral economy, hydrogen peroxide (H2O2) as futuristic energy carrier gains enormous awareness. However, seeking for stable and electrochemically selective H2O2 ORR electrocatalyst is yet a challenge, making the design of-ideally-bifunctional catalysts extremely important and outmost of interest. In this study, we explore the application of a trimetallic cobalt(II) triazole pyridine bis-[cobalt(III) corrole] complex CoIITP[CoIIIC]2 3 in OER and ORR catalysis due to its remarkable physicochemical properties, fast charge transfer kinetics, electrochemical reversibility, and durability. With nearly 100 % selective catalytic activity towards the two-electron transfer generated H2O2, an ORR onset potential of 0.8 V vs RHE and a cycling stability of 50 000 cycles are detected. Similarly, promising results are obtained when applied in OER catalysis. A relatively low overpotential at 10 mA cm-2 of 412 mV, Faraday efficiency 98 % for oxygen, an outstanding Tafel slope of 64 mV dec-1 combined with superior stability.

Electrochemical organic reactions: A tutorial review.

Although the core of electrochemistry involves simple oxidation and reduction reactions, it can be complicated in real electrochemical organic reactions. The principles used in electrochemical reactions have been derived using physical organic chemistry, which drives other organic/inorganic reactions. This review mainly comprises two themes: the first discusses the factors that help optimize an electrochemical reaction, including electrodes, supporting electrolytes, and electrochemical cell design, and the second outlines studies conducted in the field over a period of 10 years. Electrochemical reactions can be used as a versatile tool for synthetically important reactions by modifying the constant electrolysis current.

Recent Progress in (Photo-)-Electrochemical Conversion of CO2 With Metal Porphyrinoid-Systems.

Since decades, the global community has been facing an environmental crisis, resulting in the need to switch from outdated to new, more efficient energy sources and a more effective way of tackling the rising carbon dioxide emissions. The activation of small molecules such as O2, H+, and CO2 in a cost-and energy-efficient way has become one of the key topics of catalysis research. The main issue concerning the activation of these molecules is the kinetic barrier that has to be overcome in order for the catalyzed reaction to take place. Nature has already provided many pathways in which small molecules are being activated and changed into compounds with higher energy levels. One of the most famous examples would be photosynthesis in which CO2 is transformed into glucose and O2 through sunlight, thus turning solar energy into chemical energy. For these transformations nature mostly uses enzymes that function as catalysts among which porphyrin and porphyrin-like structures can be found. Therefore, the research focus lies on the design of novel porphyrinoid systems (e.g. corroles, porphyrins and phthalocyanines) whose metal complexes can be used for the direct electrocatalytic reduction of CO2 to valuable chemicals like carbon monoxide, formate, methanol, ethanol, methane, ethylene, or acetate. For example the cobalt(III)triphenylphosphine corrole complex has been used as a catalyst for the electroreduction of CO2 to ethanol and methanol. The overall goal and emphasis of this research area is to develop a method for industrial use, raising the question of whether and how to incorporate the catalyst onto supportive materials. Graphene oxide, multi-walled carbon nanotubes, carbon black, and activated carbon, to name a few examples, have become researched options. These materials also have a beneficial effect on the catalysis through for instance preventing rival reactions such as the Hydrogen Evolution Reaction (HER) during CO2 reduction. It is very apparent that the topic of small molecule activation offers many solutions for our current energy as well as environmental crises and is becoming a thoroughly investigated research objective. This review article aims to give an overview over recently gained knowledge and should provide a glimpse into upcoming challenges relating to this subject matter.

Selective and Additive-Free Hydrogenation of Nitroarenes Mediated by a DMSO-Tagged Molecular Cobalt Corrole Catalyst.

We report on the first cobalt corrole that effectively mediates the homogeneous hydrogenation of structurally diverse nitroarenes to afford the corresponding amines. The given catalyst is easily assembled prior to use from 4-tert-butylbenzaldehyde and pyrrole followed by metalation of the resulting corrole macrocycle with cobalt(II) acetate. The thus-prepared complex is self-contained in that the hydrogenation protocol is free from the requirement for adding any auxiliary reagent to elicit the catalytic activity of the applied metal complex. Moreover, a containment system is not required for the assembly of the hydrogenation reaction set-up as both the autoclave and the reaction vessels are readily charged under a regular laboratory atmosphere.

Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex.

The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular MnIII -corrole complex, which is modified on the three meso-positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO2 . Electrochemical reduction of MnIII leads to an electroactive MnII species, which binds CO2 and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO2 to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h-1 , when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the MnIII -corrole center.

Molecular cobalt corrole complex for the heterogeneous electrocatalytic reduction of carbon dioxide.

Electrochemical conversion of CO2 to alcohols is one of the most challenging methods of conversion and storage of electrical energy in the form of high-energy fuels. The challenge lies in the catalyst design to enable its real-life implementation. Herein, we demonstrate the synthesis and characterization of a cobalt(III) triphenylphosphine corrole complex, which contains three polyethylene glycol residues attached at the meso-phenyl groups. Electron-donation and therefore reduction of the cobalt from cobalt(III) to cobalt(I) is accompanied by removal of the axial ligand, thus resulting in a square-planar cobalt(I) complex. The cobalt(I) as an electron-rich supernucleophilic d8-configurated metal centre, where two electrons occupy and fill up the antibonding dz2 orbital. This orbital possesses high affinity towards electrophiles, allowing for such electronically configurated metals reactions with carbon dioxide. Herein, we report the potential dependent heterogeneous electroreduction of CO2 to ethanol or methanol of an immobilized cobalt A3-corrole catalyst system. In moderately acidic aqueous medium (pH = 6.0), the cobalt corrole modified carbon paper electrode exhibits a Faradaic Efficiency (FE%) of 48 % towards ethanol production.

Unraveling the Oxidation and Spin State of Mn-Corrole through X-ray Spectroscopy and Quantum Chemical Analysis.

The interplay between Mn ions and corrole ligands gives rise to complex scenarios regarding the metal centers' electronic properties expressing a range of high oxidation states and spin configurations. The resulting potential of Mn-corroles for applications such as catalysts or fuel cells has recently been demonstrated. However, despite being crucial for their functionality, the electronic structure of Mn-corroles is often hardly accessible with traditional techniques and thus is still under debate, especially under interfacial conditions. Here, we unravel the electronic ground state of the prototypical Mn-5,10,15-tris(pentafluorophenyl)corrole complex through X-ray spectroscopic investigations of ultrapure thin films and quantum chemical analysis. The theory-based interpretation of Mn photoemission and absorption fine structure spectra (3s and 2p and L2,3-edge, respectively) evidence a Mn(III) oxidation state with an S = 2 high-spin configuration. By referencing density functional theory calculations with the experiments, we lay the basis for extending our approach to the characterization of complex interfaces.