Construction of Metal-Coordinated Bipyridine-Based Conjugated Microporous Polymers as Robust Electrocatalysts for Hydrogen Evolution

High Resolution Image Download MS PowerPoint Slide Employing water splitting (WS) to develop electrocatalysts for the hydrogen evolution reaction (HER) presents a promising strategy for generating cost-effective energy. In recent years, extensive research has focused on designing metal-based conjugated microporous polymers (CMPs) catalysts with abundant electrocatalytically active sites, offering an efficient substitute for precious metal-based Pt/C catalysts. In this study, a series of microporous pyrene-metal CMPs (Ru, Fe, Co, and Ni) were synthesized via a one-pot Schiff-base [4 + 2] condensation reaction between 4,4’,4’’,4’’’-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetraaniline [PyBZ-TB-4NH 2 ] and [2,2’-bipyridine]-5,5′-dicarbaldehyde [BPy-2CHO] in the presence of different derivatives of transition metal salts (Ru, Fe, Co, Ni) to afford PyBZ-TB-BPy-M CMPs. The uncoordinated PyBZ-TB-BPy CMP and coordinated PyBZ-TB-BPy-M CMPs were investigated for their electrochemical HER performance. Notably, PyBZ-TB-BPy-Ru CMP exhibited an impressively minimal overpotential of 285 mV (at 10 mA cm –2 ) and a charge transfer resistance (R ct ) of 245 Ω at 280 mV overpotential in 1 M KOH electrolyte. Furthermore, PyBZ-TB-BPy-Ru CMP demonstrated excellent stability, maintaining its electrocatalytic activity with minimal performance degradation after 18 h of chronoamperometry. Additionally, PyBZ-TB-BPy-Fe, PyBZ-TB-BPy-Co, and PyBZ-TB-BPy-Ni CMPs displayed enhanced electrocatalytic activity compared to the PyBZ-TB-BPy CMP. The exceptional performance of these metal-coordinated PyBZ-TB-BPy-M CMPs highlights their potential as cost-effective, low-resistance electrocatalysts with highly exposed active sites for efficient alkaline HER.