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When solid-state redox-driven phase transformations are associated with mass loss, vacancies are produced that develop into pores. These pores can influence the kinetics of certain redox and phase transformation steps. We investigated the structural and chemical mechanisms in and at pores in a combined experimental-theoretical study, using the reduction of iron oxide by hydrogen as a model system. The redox product (water) accumulates inside the pores and shifts the local equilibrium at the already reduced material back toward reoxidation into cubic Fe_{1-x}O (where x refers to Fe deficiency, space group Fm3[over ¯]m). This effect helps us to understand the sluggish reduction of cubic Fe_{1-x}O by hydrogen, a key process for future sustainable steelmaking.
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http://dx.doi.org/10.1103/PhysRevLett.130.168001 | DOI Listing |
Inorg Chem
August 2025
GFZ Helmholtz Centre for Geosciences, Telegrafenberg, 14473 Potsdam, Germany.
We document a solid-state, temperature-dependent (25-700 °C), multistage redox transformation of crystalline ferrous iron phosphate, vivianite (Fe(PO)·8HO). Under anoxic conditions, vivianite breaks down at > 250 °C into an anhydrous, amorphous intermediate Fe(PO) phase, yet the bulk shape and morphology of the starting vivianite crystals were retained. This amorphous intermediate phase remained stable until > 500 °C, after which a redox-dependent crystallization into two different minerals was observed.
View Article and Find Full Text PDFEnviron Geochem Health
August 2025
Graduate Program in Agronomy, Federal University of Espírito Santo, Alegre, Espírito Santo, 29500-000, Brazil.
The collapse of the Fundão tailings dam in 2015 triggered widespread contamination across the Doce River basin, yet its long-term effects on lacustrine environments remain poorly understood. This study investigates how sediment mineralogy influences the retention and mobility of potentially toxic elements (PTEs) in shallow and deep lakes of the Lower Doce River. Between 2018 and 2019, bottom sediment samples (0-5 cm) were collected from three deep lakes (Limão, Nova, and Juparanã) and three shallow lakes (Areão, Areal, and Monsarás).
View Article and Find Full Text PDFNat Commun
August 2025
Department of Physics, Pusan National University, Busan, Korea.
Oxygen-vacancy engineering in transition metal oxides enables programmable functionalities by modulating the valence states and local coordination of constituents. Here, we report the selective reduction of cobalt ions in epitaxial SrFeCoO thin films under reducing gas environments, while iron ions remain unchanged. X-ray absorption spectroscopy reveals an absorption edge shift of 1.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Mechanical Engineering & Materials Science and Engineering Program, State University of New York at Binghamton, Binghamton, New York 13902, United States.
Using in situ synchrotron X-ray diffraction, we interrogate the microstructural and phase evolution of polycrystalline nickel (Ni) during redox cycling in O, H, and HO environments. Oxidation in O promotes strong (111) texturing in both the NiO overlayer and the underlying Ni substrate. However, this crystallographic alignment is lost following reduction in H and subsequent reoxidation, demonstrating irreversible microstructural changes.
View Article and Find Full Text PDFMaterials (Basel)
June 2025
Department of Geology, Faculty of Geology, University of Oviedo, C. Jesús Arias de Velasco s/n, 33005 Oviedo, Spain.
This work investigated the structural response and phase transformation dynamics of silica-bearing cherts subjected to high-temperature processing (up to 1400 °C) and prolonged mechanochemical activation. Through a combination of X-ray diffraction (XRD) with Rietveld refinement, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transmission electron microscopy (HRTEM), we trace the crystallographic pathways of quartz, moganite, tridymite, and cristobalite under controlled thermal and mechanical stress regimes. The experimental results demonstrated that phase behavior is highly dependent on intrinsic properties such as initial phase composition, impurity presence, and crystallinity.
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