Hydrophobic Coatings with Charge Permeability via Plasma Deposition of Long-Chain Perfluorocarbons.

Hydrophobization of nanotextured catalyst materials is a promising route to enhance the yield of N2 and CO2 conversion into green fuels. However, these applications require a hydrophobic coating to not only promote air trapping but also allow charge transfer at the electrode-electrolyte interface. In this work, nano thin films with thicknesses as low as 7 nm were deposited from the plasma phase of perfluorohexene, perfluorodecene, and perfluorooctane (PFO) precursors using a mild vacuum and gentle powers. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) characterization reveal that the resulting films are conformal and hydrophobic thanks to a good retention of CF2 and CF3 moieties. The PFO films exhibited the highest water contact angle and achieved superhydrophobic states when deposited on top of re-entrant nano features, an indication of successful air trapping. Electrochemical studies further demonstrated that the plasma-deposited PFO films allow charge transfer but could only sustain repeated cyclic voltammetry cycles without losing their hydrophobicity when deposited under optimal conditions. This result indicates that plasma deposition could become a viable route for the hydrophobization of electrocatalysts required to enhance the yield of poorly soluble gas reduction reactions.

Recovery of europium from E-waste using redox active tetrathiotungstate ligands.

Rare-earth elements (REEs) are critical to our modern economy, yet their mining from natural ores bears a profound environmental impact. Traditional separation techniques are chemical and energy-intensive because their chemical similarities make REEs very challenging to purify, requiring multiple extraction steps to achieve high purity products. This emphasizes the need for sustainable and straightforward separation methods. Here we introduce a strategy for the direct separation of europium (Eu) from complex mixtures under ambient conditions, leveraging on the redox non innocence of purely inorganic tungsten tetrathiolate (WS42-) ligands. The recovery of Eu is achieved upon reduction of Eu(III) to a Eu(II) coordination polymer, driven by an induced internal electron transfer from the tetrathiotungstate ligand. Applying this strategy to unconventional feedstock such as spent energy-saving lamps allows selective europium recovery with separation factors over 1000 and recovery efficiency as high as 99% without pre-treatment of the waste.

Electrocatalytic Conversion of Small Molecules Utilizing Concerted Proton-electron Transfer Mediators.

Activation of small molecules such as CO2, N2 or organic substrates and their subsequent transformation into complex value-added chemicals by electrocatalysis, utilizing renewable energy sources under ambient conditions, has gained considerable interest in the last few years. However, activation of these chemically inert molecules is hindered by their intrinsically high activation energy barrier presupposing the development of tailored catalytic systems, often precluding selective transformation to the desired target products. Recent studies have shown that the utilization of concerted proton-electron transfer (CPET) mediators (med-H) may facilitate these challenging electrocatalytic reactions.

Gauging Iron-Sulfur Cubane Reactivity from Covalency: Trends with Oxidation State.

We investigated room-temperature metal and ligand K-edge X-ray absorption (XAS) spectra of a complete redox series of cubane-type iron-sulfur clusters. The Fe K-edge position provides a qualitative but convenient alternative to the traditional spectroscopic descriptors used to identify oxidation states in these systems, which we demonstrate by providing a calibration curve based on two analytic methods. Furthermore, high energy resolution fluorescence detected XAS (HERFD-XAS) at the S K-edge was used to measure Fe-S bond covalencies and record their variation with the average valence of the Fe atoms. While the Fe-S(thiolate) covalency evolves linearly, gaining 11 ± 0.4% per bond and hole, the Fe-S(µ3) covalency evolves asystematically, reflecting changes in the magnetic exchange mechanism. A strong discontinuity manifested for superoxidation to the all-ferric state, distinguishing its electronic structure and its potential (bio)chemical role from those of its redox congeners. We highlight the functional implications of these trends for the reactivity of iron-sulfur cubanes.

Molecular Bio-inspired Strategies for the Design of Electrocatalytic Systems.

This perspective article delves into the realm of bio-inspired catalysis, highlighting the valuable insights gleaned from enzymatic systems for the design of advanced electrocatalysts. We focus here on three key aspects to mimic: the structure of enzymatic active sites, the essential functions to enable catalytic activity as well as key elementary steps of reaction mechanisms employed by enzymes to ensure maximum efficiency and selectivity. Our research group's contributions to these areas are highlighted, including the synthesis and catalytic activity of cobalt(III) pyridinethiolate complexes, the exploration of bimetallic sites mimicking biological carbon dioxide reductases and of all-ferrous Fe4S4 clusters as mimics of FeP active sites, and the integration of concerted proton-electron transfer (CPET) mediators for the generation of metal hydride species. We emphasize the potential of these bio-inspired approaches in advancing electrocatalyst design and their relevance to molecular catalysis.

Understanding the Synergy between Fe and Mo Sites in the Nitrate Reduction Reaction on a Bio-Inspired Bimetallic MXene Electrocatalyst.

Mo- and Fe-containing enzymes catalyze the reduction of nitrate and nitrite ions in nature. Inspired by this activity, we study here the nitrate reduction reaction (NO3 RR) catalyzed by an Fe-substituted two-dimensional molybdenum carbide of the MXene family, viz., Mo2 CTx : Fe (Tx are oxo, hydroxy and fluoro surface termination groups). Mo2 CTx : Fe contains isolated Fe sites in Mo positions of the host MXene (Mo2 CTx ) and features a Faradaic efficiency (FE) and an NH3 yield rate of 41 % and 3.2 µmol h-1 mg-1 , respectively, for the reduction of NO3 - to NH4 + in acidic media and 70 % and 12.9 µmol h-1 mg-1 in neutral media. Regardless of the media, Mo2 CTx : Fe outperforms monometallic Mo2 CTx owing to a more facile reductive defunctionalization of Tx groups, as evidenced by in situ X-ray absorption spectroscopy (Mo K-edge). After surface reduction, a Tx vacancy site binds a nitrate ion that subsequently fills the vacancy site with O* via oxygen transfer. Density function theory calculations provide further evidence that Fe sites promote the formation of surface O vacancies, which are identified as active sites and that function in NO3 RR in close analogy to the prevailing mechanism of the natural Mo-based nitrate reductase enzymes.

Mixed-metal Ionothermal Synthesis of Metallophthalocyanine Covalent Organic Frameworks for CO2 Capture and Conversion.

Phthalocyanines (PCs) are intriguing building blocks owing to their stability, physicochemical and catalytic properties. Although PC-based polymers have been reported before, many suffer from relatively low stability, crystallinity, and low surface areas. Utilizing a mixed-metal salt ionothermal approach, we report the synthesis of a series of metallophthalocyanine-based covalent organic frameworks (COFs) starting from 1,2,4,5-tetracyanobenzene and 2,3,6,7-tetracyanoanthracene to form the corresponding COFs named M-pPPCs and M-anPPCs, respectively. The obtained COFs followed the Irving-Williams series in their metal contents, surface areas, and pore volume and featured excellent CO2 uptake capacities up to 7.6 mmol g-1 at 273 K, 1.1 bar. We also investigated the growth of the Co-pPPC and Co-anPPC on a highly conductive carbon nanofiber and demonstrated their high catalytic activity in the electrochemical CO2 reduction, which showed Faradaic efficiencies towards CO up to 74 % at -0.64 V vs. RHE.

Co-Electrospun Poly(ε-Caprolactone)/Zein Articular Cartilage Scaffolds.

Osteoarthritis scaffold-based grafts fail because of poor integration with the surrounding soft tissue and inadequate tribological properties. To circumvent this, we propose electrospun poly(ε-caprolactone)/zein-based scaffolds owing to their biomimetic capabilities. The scaffold surfaces were characterized using Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, static water contact angles, and profilometry. Scaffold biocompatibility properties were assessed by measuring protein adsorption (Bicinchoninic Acid Assay), cell spreading (stained F-actin), and metabolic activity (PrestoBlue™ Cell Viability Reagent) of primary bovine chondrocytes. The data show that zein surface segregation in the membranes not only completely changed the hydrophobic behavior of the materials, but also increased the cell yield and metabolic activity on the scaffolds. The surface segregation is verified by the infrared peak at 1658 cm-1, along with the presence and increase in N1 content in the survey XPS. This observation could explain the decrease in the water contact angles from 125° to approximately 60° in zein-comprised materials and the decrease in the protein adsorption of both bovine serum albumin and synovial fluid by half. Surface nano roughness in the PCL/zein samples additionally benefited the radial spreading of bovine chondrocytes. This study showed that co-electrospun PCL/zein scaffolds have promising surface and biocompatibility properties for use in articular-tissue-engineering applications.

Probing the Role of Environmental and Sample Characteristics in Gap Mode Tip-Enhanced Raman Spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) has emerged as a powerful analytical tool for nondestructive and label-free molecular characterization at the nanoscale. However, the influence of environmental factors and sample characteristics on the occurrence of spurious signals, enhancement of TERS signals, and longevity of TERS probes is not well understood yet. Herein, we present a detailed investigation of the influence of oxygen, humidity, and atmospheric carbon contaminants on scanning tunneling microscopy-TERS (STM-TERS) measurements of self-assembled monolayer systems in ambient and inert environments. Our results reveal a consistent increase of TERS signals, significant reduction of spurious signals, and drastically improved longevity of TERS probes in the inert environment. Additionally, sample characteristics such as molecular packing, chemisorption behavior, and hydrophilicity are found to have a direct impact on signal enhancement in the TERS measurements of molecular self-assembled monolayers (SAMs). The novel insights gained in this study are expected to pave the way for a more robust data analysis and improved experimental design in the future gap mode STM- and atomic force microscopy-TERS (AFM-TERS) studies.

Electrocatalyst Microenvironment Engineering for Enhanced Product Selectivity in Carbon Dioxide and Nitrogen Reduction Reactions.

Carbon and nitrogen fixation strategies are regarded as alternative routes to produce valuable chemicals used as energy carriers and fertilizers that are traditionally obtained from unsustainable and energy-intensive coal gasification (CO and CH4), Fischer-Tropsch (C2H4), and Haber-Bosch (NH3) processes. Recently, the electrocatalytic CO2 reduction reaction (CO2RR) and N2 reduction reaction (NRR) have received tremendous attention, with the merits of being both efficient strategies to store renewable electricity while providing alternative preparation routes to fossil-fuel-driven reactions. To date, the development of the CO2RR and NRR processes is primarily hindered by the competitive hydrogen evolution reaction (HER); however, the corresponding strategies for inhibiting this undesired side reaction are still quite limited. Considering such complex reactions involve three gas-liquid-solid phases and successive proton-coupled electron transfers, it appears meaningful to review the current strategies for improving product selectivity in light of their respective reaction mechanisms, kinetics, and thermodynamics. By examining the developments and understanding in catalyst design, electrolyte engineering, and three-phase interface modulation, we discuss three key strategies for improving product selectivity for the CO2RR and NRR: (i) targeting molecularly defined active sites, (ii) increasing the local reactant concentration at the active sites, and (iii) stabilizing and confining product intermediates.

Copper(II) defect-cubane water oxidation electrocatalysts: from molecular tetramers to oxidic nanostructures.

We report on the synthesis and spectroscopic evidence for a sequence of structural transformations of a new defect-cubane type copper complex, [Cu4(pyalk)4(OAc)4](ClO4)(HNEt3), which acts as a pre-catalyst for water oxidation. In situ and post-catalytic studies showed that the tetrameric complex undergoes a structural transformation into dimeric and monomeric species, induced by water molecules and carbonate anions, respectively. Further, the observed electrocatalytic water oxidation activity has been confirmed to arise from in situ-generated Cu(II) oxidic nanostructures at the electrode interface.

Molybdenum(IV) ß-diketonate complexes as highly active catalysts for allylic substitution reactions.

The synthesis and characterization of a series of Mo(IV) bis-ß-diketonate (Rdiket, R = Me, tBu, Ph) dichloride (RMoIVCl2) and bistriflate (RMoIV(OTf)2) complexes are reported. All complexes are characterized in solid and solution state by XRD and 1H NMR spectroscopy. We demonstrate that the bistriflate complexes constitute highly active catalysts for allylic substitution reactions.

A Germapyramidane Switches Between 3D Cluster and 2D Cyclic Structures in Single-Electron Steps.

Reaction of the imidazolium-substituted iphosphate-diide, (Ipr)2 C2 P2 (IDP), with GeCl2 ⋅ dioxane and KBArF24 [(BarF24 )- =tetrakis[(3,5-trifluoromethyl)phenyl]borate)] afforded the dicationic spherical-aromatic nido-cluster [Ge(η4 -IDP)]2+ ([1]2+ ) (Ipr=1,3-bis(2,6-diisopropylphenyl)imidazolium-2-ylidene). This complex is a rare heavy analogue of the elusive pyramidane [C(η4 -C4 H4 )]. [1]2+ undergoes two reversible one-electron reductions, which yield the radical cation [2]⋅+ and the neutral GeII species 3. Both [2]⋅+ and 3 rearrange in solution forming the 2D aromatic and planar imidazolium-substituted digermolide [4]2+ and germole-diide 5, respectively. Both planar species can be oxidized back to [1]2+ using AgSbF6 . These redox-isomerizations correspond to the fundamental transformation of a 3D aromatic cluster into a 2D aromatic ring compound upon reduction and vice versa. The mechanism of these reactions was elucidated using DFT calculations and cyclic voltammetry experiments.

A complete biomimetic iron-sulfur cubane redox series.

Synthetic iron-sulfur cubanes are models for biological cofactors, which are essential to delineate oxidation states in the more complex enzymatic systems. However, a complete series of [Fe4S4]n complexes spanning all redox states accessible by 1-electron transformations of the individual iron atoms (n = 0-4+) has never been prepared, deterring the methodical comparison of structure and spectroscopic signature. Here, we demonstrate that the use of a bulky arylthiolate ligand promoting the encapsulation of alkali-metal cations in the vicinity of the cubane enables the synthesis of such a series. Characterization by EPR, 57Fe Mössbauer spectroscopy, UV-visible electronic absorption, variable-temperature X-ray diffraction analysis, and cyclic voltammetry reveals key trends for the geometry of the Fe4S4 core as well as for the Mössbauer isomer shift, which both correlate systematically with oxidation state. Furthermore, we confirm the S = 4 electronic ground state of the most reduced member of the series, [Fe4S4]0, and provide electrochemical evidence that it is accessible within 0.82 V from the [Fe4S4]2+ state, highlighting its relevance as a mimic of the nitrogenase iron protein cluster.

Highly dispersed silica-supported iridium and iridium-aluminium catalysts for methane activation prepared via surface organometallic chemistry.

The grafting of an iridium-aluminium precursor onto silica followed by thermal treatment under H2 yields small (<2 nm), narrowly distributed nanoparticles used as catalysts for methane H/D exchange. This Ir-Al/SiO2 catalyst demonstrated enhanced catalytic performances in comparison with the monometallic Ir/SiO2 analogue (TOFs of 339 h-1versus 117 h-1 respectively), highlighting the promoting effect of aluminium. TON up to 900 is obtained after 9 hours, without evidence of catalyst deactivation, and identical performances are achieved after air exposure, underlining the good robustness of both Ir-Al/SiO2 and Ir/SiO2 catalytic materials.

Electrocatalytic metal hydride generation using CPET mediators.

Transition metal hydrides (M-H) are ubiquitous intermediates in a wide range of enzymatic processes and catalytic reactions, playing a central role in H+/H2 interconversion1, the reduction of CO2 to formic acid (HCOOH)2 and in hydrogenation reactions. The facile formation of M-H is a critical challenge to address to further improve the energy efficiency of these reactions. Specifically, the easy electrochemical generation of M-H using mild proton sources is key to enable high selectivity versus competitive CO and H2 formation in the CO2 electroreduction to HCOOH, the highest value-added CO2 reduction product3. Here we introduce a strategy for electrocatalytic M-H generation using concerted proton-electron transfer (CPET) mediators. As a proof of principle, the combination of a series of CPET mediators with the CO2 electroreduction catalyst [MnI(bpy)(CO)3Br] (bpy = 2,2'-bipyridine) was investigated, probing the reversal of the product selectivity from CO to HCOOH to evaluate the efficiency of the manganese hydride (Mn-H) generation step. We demonstrate the formation of the Mn-H species by in situ spectroscopic techniques and determine the thermodynamic boundary conditions for this mechanism to occur. A synthetic iron-sulfur cluster is identified as the best CPET mediator for the system, enabling the preparation of a benchmark catalytic system for HCOOH generation.

Visualizing Surface Phase Separation in PS-PMMA Polymer Blends at the Nanoscale.

Phase-separated polymer blend films are an important class of functional materials with numerous technological applications in solar cells, catalysis, and biotechnology. These technologies are underpinned by the precise control of phase separation at the nanometer length-scales, which is highly challenging to visualize using conventional analytical tools. Herein, we introduce tip-enhanced Raman spectroscopy (TERS), in combination with atomic force microscopy (AFM), confocal Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS), as a sensitive nanoanalytical method to determine lateral and vertical phase-separation in polystyrene (PS)-poly(methyl methacrylate) (PMMA) polymer blend films. Correlative topographical, molecular, and elemental information reveals a vertical phase separation of the polymers within the top ca. 20 nm of the blend surface in addition to the lateral phase separation in the bulk. Furthermore, complementary TERS and XPS measurements reveal the presence of PMMA within 9.2 nm of the surface and PS at the subsurface of the polymer blend. This fundamental work establishes TERS as a powerful analytical tool for surface characterization of this important class of polymers at nanometer length scales.

Unexpected Disparity in Photoinduced Reactions of C60 and C70 in Water with the Generation of O2 •- or 1O2.

Well-defined fullerene-PEG conjugates, C60-PEG (1) and two C70-PEG (2 and 3 with the addition sites on ab-[6,6] and cc-[6,6]-junctions), were prepared from their corresponding Prato monoadduct precursors. The resulting highly water-soluble fullerene-PEG conjugates 1-3 were evaluated for their DNA-cleaving activities and reactive oxygen species (ROS) generation under visible light irradiation. Unexpectedly, photoinduced cleavage of DNA by C60-PEG 1 was much higher than that by C70-PEG 2 and 3 with higher absorption intensity, especially in the presence of an electron donor (NADH). The preference of photoinduced ROS generation from fullerene-PEG conjugates 1-3 via the type II (energy transfer) or the type I (electron transfer) photoreaction was found to be dependent on the fullerene core (between C60 and C70) and functionalization pattern of C70 (between 2 and 3). This was clearly supported by the electron transfer rate obtained from cyclic voltammetry data and computationally estimated relative rate of each step of the type II and the type I reactions, with the finding that type II energy transfer reactions occurred in the inverted Marcus regime while type I electron transfer reactions proceeded in the normal Marcus regime. This finding on the disparity in the pathways of photoinduced reactions (type I versus type II) provides insights into the behavior of photosensitizers in water and the design of photodynamic therapy drugs.

The Role of Early-Career Chemists in European Policy-Making.

Global societal challenges emphasize the importance of collaboration between scientists and policy-makers, while the participation of a diverse group of professionals, including early-career scientists, is critical towards a sustainable future. The European Young Chemists' Network (EYCN) has been actively working with the European Chemical Society (EuChemS) to create a platform for early-career chemists in policy advice. This article comments on the possible roles of scientists in policy-making and provides an overview of relevant initiatives and platforms at the European level that could facilitate involvement. Opportunities for participation in policy advice from the perspective of early-career chemists are discussed and examples of impact are provided, hoping to stimulate further discussions and engagement in policy-making.

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes.

Dinitrogen (N2 ) is the most abundant gas in Earth's atmosphere, but its inertness hinders its use as a nitrogen source in the biosphere and in industry. Efficient catalysts are hence required to ov. ercome the high kinetic barriers associated to N2 transformation. In that respect, molecular complexes have demonstrated strong potential to mediate N2 functionalization reactions under mild conditions while providing a straightforward understanding of the reaction mechanisms. This Review emphasizes the strategies for N2 reduction and functionalization using molecular transition metal and actinide complexes according to their proposed reaction mechanisms, distinguishing complexes inducing cleavage of the N≡N bond before (dissociative mechanism) or concomitantly with functionalization (associative mechanism). We present here the main examples of stoichiometric and catalytic N2 functionalization reactions following these strategies.