Degradation is minimized as the self-support on the utilized metal foam eliminates peeling of any powder catalyst during operation, with the open-porous nickel foam (NF) facilitating efficient mass transport. Comprehensive electrochemical and structure characterization of CoxB-O, reference Co(OH)2 as well as the complex, highly performing CoxB-[0.2]P-O samples, revealed that the enhanced catalytic activity resulted from the unique heterostructure and synergistic effects of cobalt with boron and phosphite in the electrocatalyst structure.