Article
Geochemistry & Geophysics
Colin Ferrari, Merlin Meheut, Eleonore Resongles, Remi Freydier, Corinne Casiot
Summary: This study calculated the equilibrium mass-dependent isotope fractionation factors between different antimony-bearing minerals and found that the oxidation state of antimony, the first neighbor of antimony, and the distortion of atomic antimony-oxygen polyhedrons are the main factors affecting antimony isotope fractionation. These results provide a theoretical basis for interpreting natural Sb isotope variations and suggest that Sb isotopes may be useful tracers of Sb transformation processes.
Article
Geochemistry & Geophysics
Chuan Liu, Weiqiang Li
Summary: This study investigates the effects of temperature and organic ligands on the partitioning of Mg isotopes between calcite and aqueous solutions through aragonite-to-calcite conversion experiments under hydrothermal conditions. The results show that the distribution coefficients of Mg and Sr in the solid and aqueous phases are correlated and that the Mg isotope fractionation factors increase with reaction temperature. Based on the experimental results, a temperature-dependent equation for Mg isotope fractionation between calcite and free Mg-aquo ions is proposed.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2023)
Article
Multidisciplinary Sciences
Anne-Marie Desaulty, Daniel Monfort Climent, Gaetan Lefebvre, Antonella Cristiano-Tassi, David Peralta, Sebastien Perret, Anthony Urban, Catherine Guerrot
Summary: Rechargeable lithium-ion batteries play a crucial role in the transition towards clean energy. However, ensuring the environmental and responsible sourcing of lithium is challenging. This study shows that using lithium isotope analysis can help determine the origin of lithium in batteries, providing a method for certifying the sourcing of lithium.
NATURE COMMUNICATIONS
(2022)
Article
Geochemistry & Geophysics
Mahmoud Alkhatib, Mutaz Qutob, Samia Alkhatib, Anton Eisenhauer
Summary: The study on Strontium isotope fractionation during the precipitation of strontianite revealed that the process is independent of specific precipitation rate (R*) and temperature (T) unlike calcite and aragonite. The difference in isotope composition between strontianite and bulk solution is mainly influenced by intermolecular forces in aqueous solutions and kinetic effects.
Article
Geochemistry & Geophysics
Xi Liu, Hai-Zhen Wei, A. E. Williams-Jones, Jing Ma, Jian-Jun Lu, Shao-Yong Jiang, Yin-Chuan Li, Ge Dong
Summary: This study investigates the chlorine isotope fractionation during serpentinization and hydrothermal mineralization, using density functional theory and ab initio molecular dynamics simulations. The results suggest a potential alternative for using apatite-group minerals to constrain the origin and evolution of hydrothermal fluids, alongside tracking sources of chloride in subduction zones and mineralizing fluids in ore deposits using chlorine isotopes.
Article
Geochemistry & Geophysics
Franziska M. Stamm, Merlin Meheut, Thomas Zambardi, Jerome Chmeleff, Jacques Schott, Eric H. Oelkers
Summary: Magnesium isotopes serve as a promising tool to trace silicate weathering and carbonate mineralization processes. This study explores the different chemical forms of magnesium in aqueous solutions and their effects on isotope fractionation.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Moon Kedia, K. R. Soumya, Upasana Phukon, Isha Mishra, Reema L. L. Borkar, Palanichamy Vengadeshwaran, Mamina Bhol, Malaichamy Sathiyendiran
Summary: This is a report on a double ouroboros-shaped molecular dimer that is formed from a tripodal molecule with molecular tweezers-like conformation at one end and a lone unit at the other. Two complementary tripodal molecules organize themselves into a dimer resembling two serpents biting each other's tails in a circular fashion.
Article
Materials Science, Multidisciplinary
Zhongyu Wan, Wenjun Xu, Tianyi Yang, Ruiqin Zhang
Summary: In this study, crystal structure search algorithms were used to explore the possibility of forming unique electrides in the As-Li system. It was found that under appropriate pressure, AsLi7 can exhibit superionic and plastic states, showing higher superconductivity and unusual physical phenomena compared to classical electrides. These findings contribute to the expansion of the research field on electrides.
Article
Chemistry, Physical
Jiadong Shen, Xijun Xu, Jun Liu, Zuosen Wang, Shiyong Zuo, Zhengbo Liu, Dechao Zhang, Jiangwen Liu, Min Zhu
Summary: This study synthesized a series of Fe-based materials as modified layers for battery separators, and found that the d-p band center model can reasonably combine reaction potential and performance differences, providing theoretical guidance for the design of superior Li-S batteries.
ADVANCED ENERGY MATERIALS
(2021)
Article
Geochemistry & Geophysics
Ataru Sato, Rizlan Bernier-Latmani, Masahiko Hada, Minori Abe
Summary: In this study, a steady-state model was introduced to elucidate the U isotopic fractionation during the biological reduction of U(VI) to U(IV), showing that the model can be used more generally for any U multi-step reaction following the Rayleigh model. Results revealed that the U isotopic fractionation associated with the binding of U(VI) to a cytochrome or with the reduction from U(VI) to U(V) could not be achieved solely with equilibrium fractionation and must include a kinetic isotope fractionation component.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Ravinder Konda, Mohammad Solimannejad, Ajay Chaudhari
Summary: This study investigates the hydrogen uptake capacity and equilibrium isotope effect for Be, Li, and Ti-doped closoborate (B6H6) complexes using first-principles calculations. Results show the adsorption of H-2/D-2 molecules on different complexes, and the calculated equilibrium isotope effect values for each complex. The study also reveals that D-2 binds better than H-2 to the B6H6M (M = Be, Li, and Ti) complexes.
STRUCTURAL CHEMISTRY
(2021)
Article
Geochemistry & Geophysics
Jixi Zhang, Renxue Shi
Summary: This study predicts the equilibrium isotope fractionation factors between Cd-bearing aqueous solutions and minerals. The results show significant differences in Cd isotope fractionation between the solutions and minerals, which has important theoretical implications for geochemical processes.
GEOCHEMICAL JOURNAL
(2022)
Article
Chemistry, Physical
Peng Gao, Zonghang Liu, Fuchun Zhang
Summary: This study systematically solved the electronic structure of Li-doped g-C2N monolayer and evaluated its performance in hydrogen storage using DFT computational studies. The results showed that Li-doped g-C2N has high hydrogen storage capacity and its performance can be further enhanced through modifications.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Geosciences, Multidisciplinary
James W. E. Drewitt, Geoffrey D. Bromiley
Summary: Ab initio molecular dynamics simulations were used to investigate the nature of boron incorporation in a haplobasalt melt at pressures up to 8 GPa. The results showed that the proportion of tetrahedral BO4 increased with pressure, while low B-concentration liquid simulations indicated that boron did not play a significant role as a network-forming cation. The study suggested that pressure could affect the extent of boron isotope fractionation in silicate melt.
FRONTIERS IN EARTH SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Huanhuan Liu, Qian Liu, Youshi Lan, Di Wang, Lifeng Zhang, Xian Tang, Suliang Yang, Zhifu Luo, Guoxin Tian
Summary: The speciation of borate species in 0.5 M NaClO4 solution is identified using potential titration and Raman spectroscopic titration. Five borate species and boric acid are determined and their formation constants are calculated. The vibrational modes and attributions of different borate species are determined using deconvolution of Raman spectra combined with DFT calculations.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Energy & Fuels
Piotr M. Kowalski, Zhengda He, Oskar Cheong
Summary: This paper discusses the thermodynamic properties of LixFePO4 and stabilizing zirconia compounds, showing different chemical characteristics under various conditions and having the potential for widespread application in energy storage.
FRONTIERS IN ENERGY RESEARCH
(2021)
Article
Chemistry, Physical
Julia M. Leys, Yaqi Ji, Martina Klinkenberg, Piotr M. Kowalski, Hartmut Schlenz, Stefan Neumeier, Dirk Bosbach, Guido Deissmann
Summary: Single-phase monazite-type ceramics, such as SmPO4, are potential host matrices for storing separated plutonium and minor actinides. This study investigated the behavior of irradiated SmPO4 and found that it has a high potential for withstanding amorphization.
Article
Chemistry, Applied
Yanyan Cui, Parvathy Anitha Sukkurji, Kai Wang, Raheleh Azmi, Alexandra M. Nunn, Horst Hahn, Ben Breitung, Yin-Ying Ting, Piotr M. Kowalski, Payam Kaghazchi, Qingsong Wang, Simon Schweidler, Miriam Botros
Summary: With the recent development of high entropy materials, an alternative approach to develop advanced functional materials with distinctive properties that show improved values compared to conventional materials has been provided. High entropy fluorides (HEFs) have been successfully synthesized and utilized as cathode materials for lithium-ion batteries, exhibiting high specific capacities and improved electrochemical properties. By altering the elemental composition, new materials with improved electrochemical performance can be designed.
JOURNAL OF ENERGY CHEMISTRY
(2022)
Article
Chemistry, Physical
Oskar Cheong, Michael H. Eikerling, Piotr M. Kowalski
Summary: Classical molecular dynamics simulations were performed to compare water structures with ab initio molecular dynamics simulations. Good agreement was found between the two approaches at the same length and time scales. However, longer trajectories simulated with classical molecular dynamics led to the formation of different, more stable water structures, which were validated with ab initio calculations. This suggests the usefulness and advantage of classical molecular dynamics simulations for sampling more realistic time and length scales in simulations of metal-aqueous solution interfaces.
APPLIED SURFACE SCIENCE
(2022)
Article
Materials Science, Multidisciplinary
Gabriel L. Murphy, Zhaoming Zhang, Helen E. Maynard-Casely, Joshua Stackhouse, Piotr M. Kowalski, Thomas Vogt, Evgeny Alekseev, Brendan J. Kennedy
Summary: A combined experimental and theoretical investigation was conducted to study the compressibility of two SrUO4-x polymorphs (alpha and fi) under hydrostatic conditions. The study explains the contrasting chemical and mechanical behaviors of these polymorphs by differences in oxygen defect formation chemistry. The experimental data and ab initio calculations revealed that the expansion of the uranyl bonds in alpha-SrUO4 and fi-SrUO4 under hydrostatic pressures is due to the reduction of uranium formal oxidation state and the formation of oxygen vacancies. The difference in preferred lattice sites for oxygen defect formation leads to the significant difference in apparent bulk moduli between the two polymorphs.
Article
Electrochemistry
Yin-Ying Ting, Piotr M. Kowalski
Summary: This study tests the performance of the parameter-free DFT+U method in predicting the structural parameters and electronic configuration of three materials. The obtained results are consistent with more computationally demanding methods. The study emphasizes the importance of using a realistic representation of the d orbitals to obtain accurate occupancies and improve the description of the electronic structure.
ELECTROCHIMICA ACTA
(2023)
Article
Multidisciplinary Sciences
Zheng-Da He, Rebekka Tesch, Mohammad J. Eslamibidgoli, Michael H. Eikerling, Piotr M. Kowalski
Summary: The doping of Fe at low concentrations enhances the electrocatalytic performance of NiOOH for the oxygen evolution reaction (OER). The existence of Fe in a low-spin state explains the large solubility limit of Fe and similarity of FeO and Ni-O bond lengths in the Fe-doped NiOOH phase. The transition from low-spin to high-spin state at around 25% Fe concentration is consistent with the experimentally determined solubility limit of Fe in NiOOH. The computed thermodynamic overpotentials for doped and pure materials are in good agreement with the measured values, indicating the key role of the low-spin state of Fe in the OER activity of Fe-doped NiOOH electrocatalysts.
NATURE COMMUNICATIONS
(2023)
Article
Geography, Physical
Niklas Wehmann, Christoph Lenting, Sandro Jahn
Summary: Calcium sulfates, such as gypsum, play important roles in industrial processes and the global sulfur cycle. Understanding the formation and transformation processes of calcium sulfate minerals, especially the reaction from gypsum to anhydrite, is still limited. Recent research suggests the significance of solution flow in facilitating anhydrite precipitation, but it is not the sole catalyst.
GLOBAL AND PLANETARY CHANGE
(2023)
Article
Multidisciplinary Sciences
James W. E. Drewitt, Adrian C. Barnes, Sandro Jahn, Richard A. Brooker, Louis Hennet, Daniel R. Neuville, Henry E. Fischer
Summary: The structure of aerodynamically levitated liquid FeAl2O4 was studied using neutron diffraction and molecular dynamics simulations, and it was found to be an ionic liquid without any preference for specific structural motifs.
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Bart Verlinden, Karen Van Hecke, Andreas Wilden, Giuseppe Modolo, Koen Binnemans, Thomas Cardinaels, Piotr M. Kowalski
Summary: In this paper, the radiolytic degradation of diglycolamides was analyzed using computational chemistry methods, focusing on structural and thermodynamic aspects. The most vulnerable parts of the organic ligands prone to attack and degradation by radicals were identified through electronic density and bond strength analysis. By computing free energy, a possible degradation path involving the breaking of the C-O bond by H radical attack was obtained. Solvation effects, including solvation entropy effects, were taken into account to investigate realistic reaction conditions. The resulting degradation mechanism is consistent with experimentally observed degradation products.
Review
Chemistry, Physical
Tobias Binninger, Piotr M. Kowalski, Michael H. Eikerling
Summary: This review provides an overview of recent progress in OER electrocatalysis, with a specific focus on computational studies that explicitly considered the elementary step of O2 desorption. It highlights the computational and methodological complexities that led to the neglect of this step in previous studies.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Yucheng Hao, Gabriel L. Murphy, Philip Kegler, Yan Li, Piotr M. Kowalski, Simon Blouin, Yang Zhang, Shuao Wang, Lars Robben, Thorsten M. Gesing, Evgeny Alekseev
Summary: A novel polymorph of ThB2O5, beta-ThB2O5, has been successfully synthesized under high-temperature high-pressure conditions. Experimental and computational results show that beta-ThB2O5 is the preferred phase under high-temperature high-pressure conditions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Christoph J. Sahle, Emmanuelle de Clermont Gallerande, Johannes Niskanen, Alessandro Longo, Mirko Elbers, Martin A. Schroer, Christian Sternemann, Sandro Jahn
Summary: This study investigates the hydration of ions in aqueous solutions using a combined experimental and theoretical approach. By analyzing the oxygen K-edge X-ray excitation spectra, the researchers were able to identify and characterize the hydration shells of Na+ and Cl- ions. The strongest spectral changes were found to originate from the first hydration shells of both ions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
Rebekka Tesch, Piotr M. Kowalski
Summary: In this study, the Hubbard U parameters for transition metals were systematically calculated using different methods, and it was found that using a more realistic projection method produced results that were more in line with experimental data and consistent with other approaches.
Article
Chemistry, Multidisciplinary
Bart Verlinden, Karen Van Hecke, Andreas Wilden, Michelle Hupert, Beatrix Santiago-Schuebel, Richard J. M. Egberink, Willem Verboom, Piotr M. Kowalski, Giuseppe Modolo, Marc Verwerft, Koen Binnemans, Thomas Cardinaels
Summary: Reprocessing of spent nuclear fuel aims to improve resource efficiency and reduce radiotoxicity and heat production. The stability of a new ligand under ionizing radiation conditions was studied, and its degradation rate was found to be lower.
Article
Geochemistry & Geophysics
Xinze Lu, Geoffrey J. Gilleaudeau, Brian Kendall
Summary: The Late Ordovician mass extinction is the first major extinction event in the Phanerozoic, but the reasons for the decline in global biodiversity before the extinction are not well understood.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2024)
Article
Geochemistry & Geophysics
Junyao Kang, Daniel D. Gregory, Benjamin Gill, Shiqiang Huang, Changxin Lai, Zhaoshan Chang, Huan Cui, Ivan Belousov, Shuhai Xiao
Summary: Sedimentary pyrite is an important geological archive, but it can be altered by diagenetic and hydrothermal processes. This study successfully trained machine learning algorithms to distinguish pyrite origins using trace element data. The approach was validated and applied to identify the origins of pyrite in two sedimentary successions in South China.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2024)