Polypyrrole regulates Active Sites in Co-based Catalyst in Direct Borohydride Fuel Cells

Direct borohydride fuel cells (DBFCs) convert borohydride (NaBH₄) chemical energy into clean electricity. However, catalytic active site deactivation in NaBH₄ solution limits their performance and stability. We propose a strategy to regulate active sites in Co-based catalysts using polypyrrole modification (Co-PX catalyst) to enhance electrochemical borohydride oxidation reaction (eBOR). As an anode catalyst, the synthesized Co-PX catalyst exhibits excellent eBOR performance in DBFCs, with current density of 280 mA ⋅ cm^-2 and power density of 151 mW ⋅ cm^-2, nearly twice that of the unmodified catalyst. The Co-PX catalyst shows no degradation after 120-hour operation, unlike the rapidly degrading control. In-situ electrochemical attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIRS) and density functional theory (DFT) suggest that polypyrrole-modified carbon support regulate the charge distribution, increasing oxidation state and optimizing adsorption/desorption of intermediates. A possible reaction pathway is proposed. This work presents a promising strategy for efficient polymer-modulated catalysts in advanced DBFCs.