Boosting the anti-poisoning ability of palladium towards electrocatalytic formic acid oxidation via polyphosphide chemistry

•P-Pd nanoparticles were facilely prepared based on polyphosphide chemistry.•The soluble phosphorus anion was used as both P source and reducing agent.•P significantly improves catalytic activity through size and electronic effects.•The P-Pd exhibited surprising anti-CO poisoning ability.•DFT calculations showed the indirect pathway was inhabited by P-doping.