Controlled synthesis of transition-metal hydroxides and oxides with earth-abundant elements have attracted significant interest because of their wide applications, for example as battery electrode materials or electrocatalysts for fuel generation. Here, we report the tuning of the structure of transition-metal hydroxides and oxides by controlling chemical reactions using an unfocused laser to irradiate the precursor solution. A Nd:YAG laser with wavelengths of 532 nm or 1064 nm was used. The Ni²⁺ , Mn²⁺ , and Co²⁺ ion-containing aqueous solution undergoes photo-induced reactions and produces hollow metal-oxide nanospheres (Ni_0.18 Mn_0.45 Co_0.37 O_x ) or core-shell metal hydroxide nanoflowers ([Ni_0.15 Mn_0.15 Co_0.7 (OH)₂ ](NO₃ )_0.2 ⋅H₂ O), depending on the laser wavelengths. We propose two reaction pathways, either by photo-induced redox reaction or hydrolysis reaction, which are responsible for the formation of distinct nanostructures. The study of photon-induced materials growth shines light on the rational design of complex nanostructures with advanced functionalities.

An understanding of the hierarchical nanostructure formation is of significant importance for the design of advanced functional materials. Here, we report the in situ study of lead sulfide (PbS) growth on gold (Au) nanorod seeds using liquid cell transmission electron microscopy (TEM). By tracking the formation dynamics of Au-PbS core-shell nanoparticles, we found the preferential heterogeneous nucleation of PbS on the ends of a Au nanorod prior to the development of a complete PdS shell. During PbS shell growth, drastic sulfidation of Au nanorod was observed, leading to large volume shrinkage (up to 50%) of the initial Au nanorod seed. We also captured intriguing wavy interfacial behavior, which can be explained by our DFT calculation results that the local strain gradient at the core-shell interface facilitates the mass transport and mediates reversible phase transitions of Au ↔ Au2S during the PbS shell growth.