RESUMEN
Nowadays, environmentally friendly, low-cost-effective, and sustainable electrocatalysts used widely for hydrogen and oxygen evolution reactions have come into the limelight as a new research topic for scientists. This study highlights the preparation of two unique and symmetrical dinuclear Cu (II) and Mn (III) bifunctional catalysts by a facile simple slow evaporation and diffusion route. [C32H24Cu2F4N4O4] (1) and [C32H24Mn2F4N4O4] (2) both have monoclinic (C2/c (15)) crystal systems, with oxidation states +2 and +3, respectively. Prominent SPR peaks at 372 and 412 nm indicate an M-L charge transfer transition in both complexes. The synthesized electrocatalysts display exceptional catalytic activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Complex 1 exhibits enhanced hydrogen generation in 0.5 M H2SO4 with a small overpotential of 216 mV at -10 mA cm-2 along with a significantly lower Tafel value of 97 mV/dec compared to Complex 2. Moreover, Complex 1 is highly active for the OER in 1 M KOH with a small Tafel slope of 103 mV/dec and a low overpotential of 340 mV to acquire 10 mA cm-2 current density, compared to Complex 2. Complex 1 and Complex 2 remain stable up to 20 h in acidic electrolyte and up to 36 h and 20 h in the basic electrolyte, respectively.
RESUMEN
Bioinspired, self-assembled hybrid materials show great potential in the field of energy conversion. Here, we have prepared a sonication-induced boladipeptide (HO-YF-AA-FY-OH (PBFY); AA = Adipic acid, F = l-phenylalanine, and Y = l-tyrosine) and an anchored, self-assembled nickel-based coordinated polymeric nanohybrid hydrogel (Ni-PBFY). The morphological studies of hydrogels PBFY and Ni-PBFY exhibit nanofibrillar network structures. XPS analysis has been used to study the self-assembled coordinated polymeric hydrogel Ni-PBFY-3, with the aim of identifying its chemical makeup and electronic state. XANES and EXAFS analyses have been used to examine the local electronic structure and coordination environment of Ni-PBFY-3. The xerogel of Ni-PBFY was used to fabricate the electrodes and is utilized in the OER (oxygen evolution reaction). The native hydrogel (PBFY) contains a gelator boladipeptide of 15.33 mg (20 mmol L-1) in a final volume of 1 mL. The metallo-hydrogel (Ni-PBFY-3) is prepared by combining 15.33 mg (20 mmol L-1) of boladipeptide (PBFY) with 3 mg (13 mmol L-1) of NiCl2·6H2O metal in a final volume of 1 mL. It displays an ultralow Tafel slope of 74 mV dec-1 and a lower overpotential of 164 mV at a 10 mA cm-2 current density in a 1 M KOH electrolyte, compared to other electrocatalysts under the same experimental conditions. Furthermore, the Ni-PBFY-3 electrocatalyst has been witnessed to be highly stable during 100 h of chronopotentiometry performance. To explore the OER mechanism in an alkaline medium, a theoretical calculation was carried out by employing the first-principles-based density functional theory (DFT) method. The computed results obtained by the DFT method further confirm that the Ni-PBFY-3 electrocatalyst has a high intrinsic activity toward the OER, and the value of overpotential obtained from the present experiment agrees well with the computed value of the overpotential. The biomolecule-assisted electrocatalytic results provide a new approach for designing efficient electrocatalysts, which could have significant implications in the field of green energy conversion.