Space Charge Transfer-Driven Donor–Acceptor Polymers as Nonmetal Electrocatalysts for Efficient and Stable Hydrogen Evolution

The development of efficient, low-cost, and highly stable electrocatalysts for the hydrogen evolution reaction (HER) is critical for sustainable energy conversion. Nonmetallic catalysts, particularly organic polymers, offer significant advantages in terms of cost and stability. Herein, we report a series of donor–acceptor (D–A) copolymers, P–AcX-TRZ100-X, synthesized through radical copolymerization of M-Ac (D) and M-TRZ (A) monomers. These materials leverage a space charge transfer effect for electrocatalytic HER. Among the synthesized materials, P–Ac50-TRZ50, with a balanced donor–acceptor ratio, exhibited the most outstanding performance. It achieved a current density of 10 mA cm –2 at a low overpotential of 189 mV and possessed a Tafel slope of 93 mV dec –1 . Furthermore, this nonmetallic catalyst demonstrated exceptional long-term stability, operating continuously for 200 h without significant degradation. In situ ATR-SEIRAS confirmed efficient *H adsorption at low overpotentials (−0.1 V vs RHE). Density functional theory (DFT) calculations revealed that the balanced charge transfer and redistribution between the M-Ac and M-TRZ units in P–Ac50-TRZ50 optimize the Gibbs free energy of *H adsorption. This work provides an avenue for designing high-performance nonmetallic electrocatalysts by tuning the electronic structure of D–A polymers.