In situ semi-transformation from heterometallic MOFs to Fe-Ni LDH/MOF hierarchical architectures for boosted oxygen evolution reaction.

Metal-organic frameworks (MOFs) with large surface area, abundant coordination metal centers and tunable structures are regarded as promising electrocatalysts for the water splitting reaction. However, the less accessible active sites and poor stability of MOFs hinder their potential practical applications. Hierarchical double-layer hydroxide (LDH)/MOF electrocatalysts that combine the advantages of two materials are expected to overcome these drawbacks. Herein, we develop a simple and universal strategy, in situ pseudomorphic transformation, to construct hierarchical LDH/MOF electrocatalysts. Accordingly, ultra-thin Fe-Ni LDH nanosheets are in situ produced in the heterometallic MOF during the transformation process. Profiting from the abundant metal sites and the extended electron transport channel from the inserted ultra-thin LDH arrays, the hierarchical Fe-Ni LDH/MOFs exhibit striking electrochemical activities for the oxygen evolution reaction (OER). In particular, the as-synthesized Fe-Ni LDH/MOF-b2 delivers the best OER performance, exhibiting an ultralow overpotential (255 mV at 10 mA cm-2), minimum Tafel slope (24 mV dec-1) and outstanding cycling durability. Meanwhile, the evolution process of the hierarchical Fe-Ni LDH/MOF has been monitored with the controllable in situ semi-transformation strategy. This also provides an opportunity to decipher the original active species for the OER process. Mechanism analysis indicates that the bimetallic MOF and bimetallic LDH are both active species, and the excellent OER performance of hierarchical Fe-Ni LDH/MOF could be attributed to the effect of "a whole greater than the sum of the parts".