Metal flux through consuming interfaces in ligand mixtures: boundary conditions do not influence the lability and relative contributions of metal species

In a mixture of metal ions and complexes, it is difficult to predict ecological risk without understanding the contribution of each metal species to biouptake. For microorganisms, the rate of uptake (internalization flux) has not only a major influence on the total metal flux but also on the bioavailability of the various metal species and their relative contributions to the total flux. In this paper, the microorganism is considered as a consuming interface, which interacts with the metal ion, M, via the Michaelis-Menten boundary conditions. The contribution of each metal complex to the overall metal flux, in relation to its lability, is examined for a number of important boundary parameters (the equilibrium constant K-a of metal with transport sites, internalization rate constant k(int) and total transport sites concentration {R}(t)). Computations were performed for Cu(II) complexes, in a multicomponent culture medium for microoganisms. For a one-ligand system, results were acquired using rigorous mathematical expressions, whereas approximate expressions, based on the reaction layer approximation (RLA) and rigorous numerical computations (computer codes MHEDYN and FLUXY), were employed for ligand mixtures. Under the condition of ligand excess, as often found in the natural environment, the relative contribution of each metal species to the total flux is shown to be independent of the boundary conditions. This finding has important implications, including an improved basis for relating the analytical signals of dynamic metal speciation sensors to metal bioavailability.

High-pressure NMR spectroscopic and calorimetric studies on formic acid dehydrogenation and carbon dioxide hydrogenation

Cornel Fink

Our current energy production is convenient and simple, but it is not sustainable. The negative impacts on our environment are omnipresent in the form of smog, extinction of species, and global warming. A major challenge of our generation is the transition to new, responsible methods of energy production. The maxim is renewable energy. Hydrogen could serve as an intermediary energy carrier. However, problems arise with the storage of hydrogen due to safety concerns and low volumetric energy density. The reduction of carbon dioxide (CO2) to formic acid (FA) is an elegant process to âcompressâ hydrogen by transforming it into a chemical which is easier and safer to handle. In this dissertation, catalytic FA dehydrogenation, CO2 reduction and calorimetric studies of the involved thermodynamics are described. The first chapter provides a global overview, beginning with general considerations about energy economy, then crossing over to hydrogen storage and infrastructure for a future hydrogen economy, before discussing FA as a hydrogen storage medium and summarizing the developments of FA dehydrogenation and CO2 hydrogenation. Chapter two describes different compounds we have studied as potential catalysts for FA dehydrogenation and CO2 hydrogenation. The focus is on complexes of Ir, Rh, and Ru regarding metals, and on Cp* and an ethylene-spaced diamine as ligands. Other motifs were also explored including Ru-phosphine complexes which afforded unexpected results. The most promising candidates are examined more closely. The third chapter summarizes our findings of formic acid dehydrogenation with homogeneous catalysts, presented in three parts. Each subchapter highlights a different structural feature or metal center. The first one focuses on Ir and Rh metal centers, equipped with Cp* and diamines. In the second section, we explore the catalytic performance of a RAPTA-type precatalyst, and the last one addresses our achievements with a rhodium catalyst containing Cp* and di(1-pyrazolyl)methane ligands. The catalysts were evaluated towards core properties such as stability (TON), activity (TOF) and recycling. Chapter four elucidates the interactions of FA with different solvents and additives, which influence the kinetics and thermodynamics of FA dehydrogenation and CO2 hydrogenation. NMR and FT-IR spectroscopy, conductometry, calorimetric measurements and computational methods were used to analyze the systems thoroughly. In chapter five, high-pressure calorimetric measurements are employed to quantify the actual energy balance during the endothermic process of FA dehydrogenation. For this purpose, we modified an off-the-shelf high-pressure reactor to suit our needs and constructed a thermo-controlled environment. Chapter six describes our research into catalytic CO2 hydrogenation to FA with two ruthenium-based phosphine pre-catalysts. One has three 1,4,7-triaza-9-phosphatricyclotridecane (CAP) ligands coordinated, which is a just recently described phosphine compound. The other complex is prepared via a straightforward synthesis route with an inexpensive, simple ligand. Both are stable in aqueous FA over weeks, making them potential catalysts for large-scale application.

EPFL2018

High-pressure NMR spectroscopic and calorimetric studies on formic acid dehydrogenation and carbon dioxide hydrogenation

Cornel Fink

EPFL2018