Redox-Induced Microstructure and Phase Dynamics in Nickel: Insights from In Situ Synchrotron X-ray Diffraction

作者：Shyam Bharatkumar Patel, Jianyu Wang, Xiaobo Chen, Yupeng Wu, Raúl Acevedo, K. Evans‐Lutterodt, Randall L. Headrick, Guangwen Zhou · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c06066 · 被引用次数：6 · 研究领域：Corrosion Behavior and Inhibition、Hydrogen embrittlement and corrosion behaviors in metals、nanoparticles nucleation surface interactions

Using in situ synchrotron X-ray diffraction, we interrogate the microstructural and phase evolution of polycrystalline nickel (Ni) during redox cycling in O 2, H 2, and H 2 O environments. Oxidation in O 2 promotes strong (111) texturing in both the NiO overlayer and the underlying Ni substrate. However, this crystallographic alignment is lost following reduction in H 2 and subsequent reoxidation, demonstrating irreversible microstructural changes. H 2 exposure leads to proton dissolution into the Ni lattice, triggering a localized phase transition from face-centered cubic (FCC) to hexagonal close-packed (HCP) Ni in hydrogen-saturated regions. In H 2 O-containing atmospheres, dissociative H 2 O adsorption produces protons that permeate the NiO layer, forming γ-NiOOH within the NiO lattice and HCP Ni beneath the NiO overlayer as protons accumulate. Kinetic analysis via the Johnson-Mehl-Avrami–Kolmogorov model uncovers distinct growth mechanisms: preoxidized Ni surfaces follow one-dimensional (1D) kinetics for NiO, γ-NiOOH, and HCP growth, whereas pristine Ni exhibits three-dimensional (3D) kinetics due to island-like nucleation and growth of NiO. These results highlight the critical interplay between H 2 O dissociation, hydrogen permeation, and redox-driven phase transformations, with practical implications in engineering nickel-based catalysts and hydrogen storage systems through controlled microstructural and phase evolution.