In Situ Grown Mn(II) MOF upon Nickel Foam Acts as a Robust Self-Supporting Bifunctional Electrode for Overall Water Splitting: A Bimetallic Synergistic Collaboration Strategy

The design of highly efficient, cost-effective non-noble metal-based electrocatalysts with superior stability for overall water splitting (OWS) reactions is of great importance as well as of immense challenge for the upcoming sustainable and green energy conversion technologies. Herein, a convenient and simple in situ solvothermal method has been adopted to fabricate a self-supported, binder-free 3D electrode (Mn-MOF/NF) by the direct growth of a newly synthesized carboxylate-based pristine Mn(II)-metal-organic framework (Mn-MOF) upon the conducting substrate nickel foam (NF). The binder-free Mn-MOF/NF electrode exhibits excellent performances toward OWS with ultralow overpotentials of 280 mV@20 mA cm^-2 for the oxygen evolution reaction (OER) and 125 mV@10 mA cm^-2 for the hydrogen evolution reaction (HER) with remarkable durability. Mn-MOF/NF can also attain a current density of 10 mA cm^-2 with a low cell voltage of 1.68 V in a 0.1 M KOH solution in a two-electrode system for OWS. The direct growth of nonconducting electroactive Mn-MOF materials upon conducting substrate NF provides an excellent mass transport of the electrolyte with a relatively low contact resistance due to the strong catalyst-substrate contact and enhances the efficient electron transport for OWS. The redox chemical etching of the self-sacrificial substrate NF during solvothermal synthesis introduces redox-active Ni²⁺ in Mn-MOF/NF. Thus, the excellent OWS electrocatalytic activity can mainly be attributed to the bimetallic synergistic collaboration of the two redox active metal centers (Mn²⁺ and Ni²⁺) along with the excellent support surface of NF, which provides a high specific surface area and maximum utilization of the electroactive metal ion sites by preventing the self-aggregation of the active sites. The Mn-MOF/NF electrode also exhibits superb stability and durability for a prolonged time throughout the multiple cycles of full water splitting reactions. Therefore, this work elucidates a convenient and smart approach for constructing MOF-based bifunctional electrocatalysts for OWS.