Superior Electrochemical Water Splitting and Energy-Storage Performances of In Situ Fabricated Charge-Separated Metal Organophosphonate Single Crystals

The design and exploration of advanced materials as a durable multifunctional electrocatalyst toward sustainable energy generation and storage development is the most perdurable challenge in the domain of renewable energy research. Herein, a facile in situ solvothermal approach has been adopted to prepare a methylviologen-regulated crystalline metal phosphonate compound, [C12H14N2]­[Ni­(C11H11N2)­(H2hedp)2]2•6H2O (NIT1), (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid) and well characterized by several techniques. The as-prepared NIT1 displays excellent bifunctional electrocatalytic activity with dynamic stability toward oxygen evolution reaction (η10 = 288 mV) and hydrogen evolution reaction (η10 = 228 mV) in alkaline (1.0 M KOH) and acidic mediums (0.5 M H2SO4), respectively. Such a low overpotential and Tafel slope (68 mV/dec for OER; 56 mV/dec for HER) along with long-term durability up to 20 h of NIT1 make it superior to benchmark the electrocatalyst and various nonprecious metal-based catalysts under similar experimental condition. Further, the electrochemical supercapacitor measurements (in three-electrode system) reveal that the NIT1 electrode possesses much higher specific capacity of 187.6 C g–1 at a current density of 2 A g–1 (272 C g–1 at 5 mV s–1) with capacitance retention of 75.2% over 10,000 cycles at 14 A g–1 (Coulombic efficiency > 99%) in 6 M KOH electrolyte medium. Finally for a practical application, an asymmetric supercapacitor device (coin cell) is assembled by NIT1 material. The as-fabricated device delivers the maximum energy density of 39.4 Wh kg–1 at a power density of 450 W kg–1 and achieves a wide voltage window of 1.80 V. Notably, the device endures a remarkable cycle performance with cyclic retention of 92% (Coulombic efficiency > 99%) even after 14,000 charge/discharge cycles at 10 A g–1. Nevertheless, the extraordinary electrochemical activities toward OER and HER as well as the high-performance device fabrication for LED illumination of such a noble metal-free lower-dimensional charge-transfer compound are truly path breaking and would be promising for the development of advanced multifunctional materials.