A radiochemical lab-on-a-chip paired with computer vision to unlock the crystallization kinetics of (Ba,Ra)SO4.

(Ra,Ba)SO4 solid solutions are commonly encountered as problematic scales in subsurface energy-related applications, e.g., geothermal systems, hydraulic fracturing, conventional oil and gas, etc. Despite its relevance, its crystallization kinetics were never determined because of radium (226), high radioactivity (3.7 × 1010 Bq g-1), and utilization in contemporary research, therefore constrained to trace amounts (< 10-8 M) with the composition of BaxRa1-xSO4 commonly restricted to x > 0.99. What if lab-on-a-chip technology could create new opportunities, enabling the study of highly radioactive radium beyond traces to access new information? In this work, we developed a lab-on-a-chip experiment paired with computer vision to evaluate the crystal growth rate of (Ba,Ra)SO4 solid solutions. The computer vision algorithm enhances experimental throughput, yielding robust statistical insights and further advancing the efficiency of such experiments. The 3D analysis results of the precipitated crystals using confocal Raman spectroscopy suggested that {210} faces grew twice as fast as {001} faces, mirroring a common observation reported for pure barite. The crystal growth rate of (Ba0.5Ra0.5)SO4 follows a second-order reaction with a kinetic constant equal to (1.23 ± 0.09) × 10-10 mol m-2 s-1.

Stay Hydrated! Impact of Solvation Phenomena on the CO2 Reduction Reaction at Pb(100) and Ag(100) surfaces.

Herein, a comprehensive computational study of the impact of solvation on the reduction reaction of CO2 to formic acid (HCOOH) and carbon monoxide on Pb(100) and Ag(100) surfaces is presented. Results further the understanding of how solvation phenomena influence the adsorption energies of reaction intermediates. We applied an explicit solvation scheme harnessing a combined density functional theory (DFT)/microkinetic modeling approach for the CO2 reduction reaction. This approach reveals high selectivities for CO formation at Ag and HCOOH formation on Pb, resolving the prior disparity between ab initio calculations and experimental observations. Furthermore, the detailed analysis of adsorption energies of relevant reaction intermediates shows that the total number of hydrogen bonds formed by HCOO plays a primary role for the adsorption strength of intermediates and the electrocatalytic activity. Results emphasize the importance of explicit solvation for adsorption and electrochemical reaction phenomena on metal surfaces.

Pyrochlore Compounds From Atomistic Simulations.

Pyrochlore compounds (A 2 B 2O7) have a large applicability in various branches of science and technology. These materials are considered for use as effective ionic conductors for solid state batteries or as matrices for immobilization of actinide elements, amongst many other applications. In this contribution we discuss the simulation-based effort made in the Institute of Energy and Climate Research at Forschungszentrum Jülich and partner institutions regarding reliable computation of properties of pyrochlore and defect fluorite compounds. In the scope of this contribution, we focus on the investigation of dopant incorporation, defect formation and anion migration, as well as understanding of order-disorder transitions in these compounds. We present new, accurate simulated data on incorporation of U, Np, Pu, Am and Cm actinide elements into pyrochlores, activation energies for oxygen migration and radiation damage-induced structural changes in these materials. All the discussed simulation results are combined with available experimental data to provide a reliable description of properties of investigated materials. We demonstrate that a synergy of computed and experimental data leads to a superior characterization of pyrochlores, which could not be easily achieved by either of these methods when applied separately.