In this study, new insights into the solid state chemistry of the systems NaCl-RECl3 (RE = Ce, Nd) are presented, in which the intermediate compound suggested in the literature, i.e. Na3RE5Cl18, is investigated more closely. Our studies have revealed a solubility range around the intermediate composition in the form of the stoichiometry, and have allowed us to revisit the phase diagrams of the NaCl-RECl3 (RE = Ce, Nd) systems accordingly. Furthermore, we demonstrate that among the lanthanide chlorides, NdCl3 is the prime simulant candidate for the melting behaviour of PuCl3-based systems, while CeCl3 is most suited to simulate UCl3-based systems. This is corroborated in this work by comparing the melting profiles of the NaCl-MCl3, MgCl2-MCl3, and NaCl-MgCl2-MCl3 (M = Ce, Nd, U, Pu) systems. In doing so, the binary systems MgCl2-MCl3 (M = Ce, Nd) have been re-visited based on existing data in the literature and estimated mixing enthalpies. Extrapolations to the ternary systems NaCl-MgCl2-RECl3 (RE = Ce, Nd) have been made and compared to the available data in the literature, showing good agreement.

Graphical abstract: Simulant chemistry for uranium and plutonium molten fuel salts: crystallographic investigation and thermodynamic modelling assessment of the NaCl–RECl3 and NaCl-MgCl2-RECl3 (RE = Ce, Nd) systems ... Read more

The electrochemical reduction of carbon dioxide (CO₂) to value-added chemicals is a promising strategy to mitigate climate change. Metalloporphyrins have been used as a promising class of stable and tunable catalysts for the electrochemical reduction reaction of CO₂ (CO₂RR) but have been primarily restricted to single-carbon reduction products. Here, we utilize functionalized earth-abundant manganese tetraphenylporphyrin-based (Mn-TPP) molecular electrocatalysts that have been immobilized via electrografting onto a glassy carbon electrode (GCE) to convert CO₂ with overall 94 % Faradaic efficiencies, with 62 % being converted to acetate. Tuning of Mn-TPP with electron-withdrawing sulfonate groups (Mn-TPPS) introduced mechanistic changes arising from the electrostatic interaction between the sulfonate groups and water molecules, resulting in better surface coverage, which facilitated higher conversion rates than the non-functionalized Mn-TPP. For Mn-TPP only carbon monoxide and formate were detected as CO₂ reduction products. Density-functional theory (DFT) calculations confirm that the additional sulfonate groups could alter the C−C coupling pathway from *CO→*COH→*COH-CO to *CO→*CO-CO→*COH-CO, reducing the free energy barrier of C−C coupling in the case of Mn-TPPS. This opens a new approach to designing metalloporphyrin catalysts for two carbon products in CO₂RR. ... Read more