Ligand-Assisted Controllable Growth of Self-Supporting Ultrathin Two-Dimensional Metal-Organic Framework Nanosheet...

Rational design of metal-organic frameworks (MOFs) into ultrathin two-dimensional (2D) nanosheets with controllable thickness is significantly attractive but is also a significant challenge. Herein, the authors report, for the first time, the synthesis of ultrathin 2D nickel-based MOF nanosheets with a thickness of only about 2 nm via a ligand-assisted controllable growth strategy, which cannot be acquired from the exfoliation of their bulky counterparts or the conventional hydrothermal method. The correlation between 2D nanosheets and crystal growth preference was demonstrated through a judicious choice of a specific [Ni(BIP)(p-BDC)(H₂O)₂] framework (BIP = (3,5-bis(1-imidazoly)pyridine), p-H₂BDC = terephthalic acid) to underlie the geometry of the resultant morphology. Under the modulation by the dosage of terephthalic acid through a corrosion-dissolution-coordination process, the nanosheets of Ni-MOFs with a controllable thickness can be tuned to 50 and 100 nm. Ultrathin 2D Ni-MOF nanosheet-derived N-doped Ni@carbon exhibits a satisfactory electrocatalytic performance with a small overpotential of 170 mV to achieve a current density of 10 mA cm^-2, much outperforming the bulk Ni-MOF and the most reported non-noble-metal oxygen evolution reaction electrocatalysts to date. It is believed that this ligand-assisted controllable growth strategy represents a novel and simple path to prepare high-performance MOF-based electrocatalysts for wide applications.