Structural Evolution\nStudy of Titanium–Vanadium–Niobium\nNanoparticles from Single to Multicomponent Systems

In this article, the revised basin-hopping with mirror-rotation\nsampling combined with density functional theory, which was proposed\nby our previous study, was used to study the structural property of\nTi<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7), V<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> =\n1–7), Nb<sub><i>n</i></sub> (<i>n</i> =\n3<i>m</i>, <i>m</i> = 1–7), and Ti<sub><i>n</i></sub>V<sub><i>n</i></sub>Nb<sub><i>n</i></sub> (<i>n</i> = 1–7) systems. We found\nthat equiatomic Ti<sub><i>n</i></sub>V<sub><i>n</i></sub>Nb<sub><i>n</i></sub> (<i>n</i> = 1–7)\nsystems do not change their lowest energy structures relative to the\nsame size Ti<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7), V<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7), and Nb<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7) systems,\nand this indicates that the nanoparticles composed of titanium, vanadium,\nor niobium elements may have similar energy morphologies when the\natomic number is the same. Based on the low-energy structural similarity\nof titanium–vanadium–niobium systems between single\nand multicomponent, we used the element space position replacement\n(ESPR) method to reconstruct the low-energy structure of Ti<sub><i>n</i></sub>V<sub><i>n</i></sub>Nb<sub><i>n</i></sub> (<i>n</i> = 1–7) systems. For the Ti<sub>7</sub>V<sub>7</sub>Nb<sub>7</sub> system, the average sampling step\nof 10 separate searches of the BH-MRS method is 1226 more than that\nof the ESPR method to find the lowest energy structure (six-ring layered\nstructure). The electronic property calculation shows that using equiatomic\nvanadium and niobium elements to replace titanium element in the Ti<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7) system may not change its stability,\nand the Ti<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7) system has better electron\ntrapping ability than V<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7), Nb<sub><i>n</i></sub> (<i>n</i> = 3<i>m</i>, <i>m</i> = 1–7), and Ti<sub><i>n</i></sub>V<sub><i>n</i></sub>Nb<sub><i>n</i></sub> (<i>n</i> = 1–7) systems. Our method and results\ncan be helpful for the design of nanostructures of transition metals\nwith better catalytic properties.