3D Hydrangea Macrophylla-like Nickel-Vanadium Metal-Organic Frameworks Formed by Self-Assembly of Ultrathin 2D Nanosheets for Overall Water Splitting.

The development of highly efficient and low-cost bifunctional noble metal-free electrocatalysts for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is an effective strategy for improving efficiency. Herein, novel three-dimensional (3D) bimetallic metal-organic frameworks containing Ni and V with adjustable stoichiometry were synthesized on nickel foam successfully. Notably, Ni2V-MOFs@NF only require rather low overpotentials of 244 and 89 mV for the OER and HER, respectively, and expedites overall water splitting with 1.55 V at 10 mA cm-2 with robust durability during the 80 h test. The high efficiency of the novel obtained electrocatalysts should be attributed to the particular morphological design of the two-dimensional (2D) ultrathin nanosheets self-assembling into a 3D nanoflower and the electronic structure regulation resulting from the synergetic interaction between nickel and vanadium. Subsequent theoretical calculations reveal the following conclusions: (I) the exceptional electronic conductivity of Ni2V-MOFs shows enhanced optimization as a result of electronic structure reconstruction, (II) the energy barrier reduction of the rate-limiting step is responsible for the enhanced dynamics of Ni2V-MOFs for the OER, and (III) the facilitation of the adsorption of H+ and H2O plays a key role in progressing the HER catalytic activity of Ni2V-MOFs.