Metamorphosis of Multilayered‐(NH ₄ ) ₂ V ₇ O ₁₆ Squares to Zinc Vanadate and w‐ZnO Nanoparticles via Zinc Metalation through Atomic Layer Deposition: Precision and Sustainability in Material Transformation

Vapor phase metalation (VPM) via atomic layer deposition is emerging as a sustainable, solvent‐free method for precise material functionalization. This study demonstrates selective zinc metalation of multilayered (NH 4 ) 2 V 7 O1 16 nanostructured squares using diethylzinc (DEZ) as a volatile precursor. A sequence of samples—(HDA)V 7 O 16 ·nH 2 O (S‐1), (NH 4 ) 2 V 7 O 16 ·nH 2 O (S‐2), iodine‐functionalized (S‐3), and Zn‐metalated (S‐4)—was characterised via XRD, HRTEM/SAED, FIB‐SEM, ESEM, ATR‐FTIR, Raman microscopy, and XPS. The V7 7 O 16 bilayer framework revealed a triclinic crystal structure (P‐1 space group) for the first time. VPM enabled the transformation into Zn 3 V3 3 O 8 and wurtzite ZnO nanoparticles with structural precision and minimal waste. Metalation was achieved from a single half‐cycle (210 seconds total), allowing fine control over deposition dynamics. This process also induced a magnetic transition from spin‐frustrated semiconducting behavior to ferrimagnetism. The results underscore VPM's potential for low‐impact, high‐precision synthesis of multifunctional oxides, aligning with circular economy principles by reducing waste and enhancing recyclability. Applications span spintronics, neuromorphic computing, and sustainable catalysis.