Spin-state Directed Synthesis of >20 micrometers 2D Layered Transition Metal Hydroxides via Edge-on Condensation

Layered transition metal hydroxides (LTMHs) with transition metal centers sandwiched between layers of coordinating hydroxide anions have attracted considerable interest for their potential in developing clean energy sources and storage technologies. However, two dimensional (2D) LTMHs remain largely unstudied in terms of their physical properties and the applications in electronic devices. Here, directed by the relationship of the spin state of 3d transition metal (TM) ions such as Ni, Co, Cu, and the corresponding geometry of the crystal field, we discover that Ni2+ with perfect Oh symmetry is ideal for intraplanar growth, leading to the achievement of >20 {\mu}m {\alpha}-Ni(OH)2 2D crystals with high yield, which are the largest 2D domains reported so far. We also report the successful synthesis of 2D Co(OH)2 crystals (>40 {\mu}m) with less yield due to the slight geometry distortion resulted from uneven number of electrons. Moreover, the detailed structural characterization of synthesized {\alpha}-Ni(OH)2 are performed; the optical band gap energy is extrapolated as 2.54 eV from optical absorption measurements and is measured as 2.50 eV from reflected electrons energy loss spectroscopy (REELS), suggesting the potential as insulating 2D dielectric material for electronic devices. Furthermore, key parameters of the hydrothermal reaction including soaking temperature, starting pH and cooling rate, are systematically tuned to understand their effects on morphological and crystallographic perspectives, allowing the establishment of a 2D growth mechanism. This work demonstrates a scalable pathway to synthesize large 2D LTMHs from simple methods, paving the way for the study of fundamental physical properties and device applications of 2D LTMHs.