Abstract
Zr(2)Fe alloy is a promising candidate as a tritium-getter material for the International Thermonuclear Experimental Reactor (ITER), but its practical application is hindered by undesirable inverse disproportionation behavior and poor anti-disproportionation properties. In this study, theoretical computational screening is utilized to predict the effects of partially substituting Fe with Co, Cu, and Ni on regulating the Zr(2)Fe(1-x)M(x) (M = Co, Cu, Ni; x = 0.1-0.5) hydrogen storage systems. Experimentally, these modifications successfully correct the distorted inverse disproportionation reaction and achieve full reversibility in the Zr(2)Fe(1-x)M(x-)H systems. Notably, Zr(2)Fe(0.8)Cu(0.2) and Zr(2)Fe(0.7)Ni(0.3) alloys retain excellent hydrogen storage properties, while their kinetic energy barriers of hydriding disproportionation reaction increase significantly from 87.88 kJ mol(-1) (Zr(2)Fe) to 184.35 kJ mol(-1) (Zr(2)Fe(0.8)Cu(0.2)) and 192.32 kJ mol(-1) (Zr(2)Fe(0.7)Ni(0.3)), respectively. The corresponding deceleration of hydriding disproportionation kinetics behaviors is clearly visualized by TEM observations. Combined density functional theory analyses reveal that the mechanism underlying enhanced anti-disproportionation properties in the optimized Zr(2)Fe(1-x)M(x-)H systems involves the homogenization and stabilization of Zr─H bonds within the hydrogen storage interstices, along with the effective suppression of disproportionation-favorable chemical environments.